CN102224189A - Fluoropolymer/particulate filled protective sheet - Google Patents

Fluoropolymer/particulate filled protective sheet Download PDF

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Publication number
CN102224189A
CN102224189A CN2009801468618A CN200980146861A CN102224189A CN 102224189 A CN102224189 A CN 102224189A CN 2009801468618 A CN2009801468618 A CN 2009801468618A CN 200980146861 A CN200980146861 A CN 200980146861A CN 102224189 A CN102224189 A CN 102224189A
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CN
China
Prior art keywords
film
fluoropolymer
filler material
multilayer film
curtain coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2009801468618A
Other languages
Chinese (zh)
Inventor
H·范
K·C·洪
G·S·赛克宏
K·康勒
J·迪可勒特吉布森
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Performance Plastics Corp
Original Assignee
Saint Gobain Performance Plastics Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saint Gobain Performance Plastics Corp filed Critical Saint Gobain Performance Plastics Corp
Publication of CN102224189A publication Critical patent/CN102224189A/en
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/41—Opaque
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/416—Reflective
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
    • Y10T428/31544—Addition polymer is perhalogenated

Landscapes

  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention describes a particulate filled film, useful as a backsheet for a photovoltaic construct.

Description

The protectiveness sheet material that fluoropolymer/particulate is filled
The cross reference of related application
The application requires in the U.S. Provisional Application sequence number 61/104 of submission on October 13rd, 2008; 914 name be called " the protectiveness sheet material that fluoropolymer/particulate is filled " and on August 10th, 2009 submit to 61/232; 694 name is called the right of priority and the rights and interests of " fluoropolymer film ", for all purposes are combined in this with it by reference in full with its content.
Invention field
Present invention relates in general to have at least a particulate and imbed film and multilayer film in the film and the method that is used to make them, these films and multilayer film are useful as wrapping material.
Background of invention
Multilayer film or laminated material are to attempt the characteristic of different layers is merged so that compare such structure that independent material provides a kind of improved performance.The characteristic of making us wishing for multilayer film comprises moisture barrier, weathering resistance, anti-color or other two sides electromagnetic spectrum effects of cutting the general character, resistive, surface reflection, opacity, two sides.
Till the present invention, this type of laminated material often cause characteristic imbalance, be expensive or be difficult to handle or process.Add a kind of material and improve the loss that a specific character may cause taking place simultaneously another kind of characteristic.
In the field of cumulative Electronic Protection packaging film, importantly provide the balance a kind of good customization, economy of desired characteristic.For example, be used for the combination that liner film after the protectiveness of photovoltaic device must provide multifrequency nature (for example preventing moisture, good dielectric strength, high opacity and/or reflectivity).Realize that in a kind of multilayer film these characteristics are difficulties or expensive always.
Particularly, realize that by the common method that adds a kind of suitable weighting agent Characteristics Control causes improvement on the specific character to be accompanied by the decline of another kind of characteristic through regular meeting.For example, add a kind of undesirable increase that the light weighting agent can cause moisture steam transmitance that hinders to obtain the needed level of high-caliber opaqueness.Similarly, add undesirable reduction that high-caliber resistance light weighting agent can cause dielectric strength.In another example, add weighting agent and can produce a bad multilayer film surface of adhesivity in being incorporated into photovoltaic device the time with the reflectivity that increases a kind of film.Previous film generally provides the characteristic of one or both hope of the protectiveness film that is used for electronic installation, but a kind of Combined Protection of better level can not be provided always.
In addition, when weighting agent being added in the multilayer film that melt extrude, they can be difficult to disperse, thereby require considerable mixing, and this has caused the increase of treatment time and expense.
Therefore, there are a kind of needs for being customized for the photovoltaic sheet material provides one or more multilayer film that improve characteristic.For for also there are a kind of needs in the multilayer film of other protectiveness applied customizations, it is for example to be used for the protectiveness film that protectiveness that lead or cable use held or be used for other opto-electronic devices such as OLEDS that these protectiveness are used.
The invention summary
The present invention unexpectedly provides or the multilayer film of multinomial shortcoming and the method for preparing these type of multilayer film known in the art of having overcome.Have been found that and to make and use the have multifrequency nature multilayer film of (for example being suitable for being used for the wrapping material of electron device).These films help these parts of protection to avoid heat, humidity, chemical, radiation, physical hazard and general wearing and tearing.This kind wrapping material help to make the active parts/circuit electrical isolation of these electron devices.In addition, this type of material provides the protective cushion to electron device (for example photovoltaic device), and flame retardant resistance, aesthetic beauty and/or the opacity of anti-soil characteristic, chemical resistant properties, anti-UV, reflectivity, increase is provided.
On the one hand, the invention provides a kind of curtain coating composition, said composition comprises: a kind of carrier liq; A kind of polymer resin matrix material; A kind of particulate filler material; And wherein this matrix material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material volume percent of different weight percentage.
Unexpectedly, have been found that by selecting one or more in the following parameter, can control the opaqueness of this film and the outward appearance of aesthetic pleasant is provided simultaneously and film integrity is provided, these parameters are: the type of the dimension of particulate weighting agent, particulate weighting agent and/or the volume percent of filler material.In general, by mixing particulate weighting agent still less, on the integrity of film, exist and improve and kept opaqueness simultaneously.The particulate weighting agent of lower level can also provide lower moisture transmission or the improvement on the dielectric strength.Therefore, in certain embodiments, the weighting agent less than 15 volume percent is present in the final film.
Although interesting, found volume percent for the control weighting agent, there is the balance of a plurality of factors.Granularity also can influence the globality of film and in some respects, and the operator will be chosen in none in the particulate single linear dimension wherein greater than 10 μ m and can be one or more filler materials from a nanometer (nm) to about 100nm (for example 0.1 μ m).On the other hand, this particulate weighting agent can have from the one-dimensional degree of 100nm to 2 μ m.In other respects, some in this particulate weighting agent can have the single linear dimension greater than 10 μ m.
The selection of particulate itself can help to improve film integrity and physical property, as opacity, steam breathability, IR reflectivity and specific inductivity.This particulate can be the wherein a kind of of and the following or their mixture: silica granule, aluminum slice, glass beads, glass microsphere, glass fibre, titanium dioxide granule, barium titanate particles, lime carbonate, zinc oxide, mica, clay (as kaolin or other materials), mullite, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, a series of pigment such as aluminic acid cobalt blue, sulphur sodium silicoaluminate (sodium alumino sulphosilicate), fire retardant class such as magnesium hydroxide, antimonous oxide, the compound of organophosphate or bromination, or be appropriate to other particulates of the set application of expecting.In some embodiments, granularity can be from about 100 nanometers (nm) to about 2 microns (μ m).
On the other hand, this particle may be reflexive in the spectrographic region of ultra-red.Aspect the thermal accumlation of such particle in reducing IR absorption and this film therefore can be effectively, has allowed a series of colors in the visible spectrum to select with same selection simultaneously.This type of IR reflective pigments comprises the Company from Shepherd Color, Cincinnati, (Arctic Black) 10C909, black 411, yellow 193, brown 12 and brown 8 is deceived in the arctic of OH, and from Ferro Corporation, the V-780 of Cleveland OH is black, V-778 is black, PC-9415 is yellow, V-9248 is blue, V-13810 is red and the V-12600 camouflage color is green.
On the other hand, the invention provides film from this curtain coating composition.
On the other hand, the invention provides the method for preparation film disclosed here and multilayer film.
Still aspect another, the invention provides a kind of photovoltaic device, this photovoltaic device comprises a photovoltaic component by a film of the present invention or multilayer film protections (for example contacting with it).
It should be understood that multilayer film of the present invention can comprise from 2 to about 12 material layers.For example, these multilayer film can repeat the shop layer of a first layer and a second layer, and are like that.In the structure of these multilayer film, can comprise a skin or two skins.For example, these skins can be a kind of fluoropolymer or non-fluorinated polymer.In addition, comprised the combination of different layers at this, for example, the first layer, second layer, one be different from this first or the 3rd layer and of the second layer be different from this first, second or the trilaminar the 4th layer, or the like.Equally, this shop layer can carry out repetition on demand for contemplated application.
When multilayer film have between about 0.8 mil and about 2.0 mils, for example during the thickness of about 1.1 mils, these multilayer film have generally the dielectric breakdown strength greater than 3kV (kV) measured by ASTM method D3755, by ASTM method E424 measure greater than 70% solar reflectance or by ASTM method F1249 measure less than 20g/m 2The steam permeating rate in/sky.
The present invention also provides preparation to run through the method for these pointed multilayer film of this specification sheets.
Although disclosed a plurality of embodiments, the present invention still has other embodiments will become clear from following detailed description for the ordinary skill in the art.Be as will be clear, the present invention can have change aspect conspicuous different, and all these changes all do not deviate from the spirit and scope of the present invention.Therefore, should to be considered to be illustrative and nonrestrictive in itself in these detailed descriptions.
Describe in detail
In this specification sheets and claim, term " comprises " and " comprising " is open term and should be interpreted as being meant " including but not limited to ... ".These terms contain restrictive term " basically by ... form " and " by ... form ".
Must be pointed out that as using at this and in claims, unless context is definite clearly in addition, otherwise singulative " a kind of/one (a/an) " and " being somebody's turn to do (the) " comprise that plural number refers to.Similarly, these terms " a kind of ", " one or more " and " at least one " can use interchangeably at this.It should still be noted that term " comprises ", " comprising ", " it is characterized by " and " having " can use interchangeably.
Unless otherwise defined, all technology as used herein and term science all have the identical implication with those skilled in the art's common sense.For all purposes, all be combined in this in full with it by reference in these all publications definitely mentioned and patent, these purposes comprise explanation and disclose chemical, instrument, statistical study and methodology (they are reported) in the publications of may be related to the present invention and using.All reference of quoting in this manual all should be considered to show the state of the art of this area.Anything all should not be construed as and is to recognize that the present invention does not have qualification owing to formerly invent prior to this type of disclosure at this.
The present invention includes different embodiments.In one first embodiment, the present invention relates to a kind of curtain coating composition, comprising:
A kind of carrier liq;
A kind of non-fluorinated polymer of non-fibrillation or fluoropolymer matrix (a kind of fluoropolymer resin or polymeric matrix) material;
A kind of particulate filler material, wherein some particles of this particulate filler material present a single linear dimension greater than 10 μ m; And wherein this matrix material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent.
In one second embodiment, the present invention relates to a kind of curtain coating composition, comprising:
A kind of carrier liq;
A kind of non-fluorinated polymer of non-fibrillation or fluoropolymer substrate material;
A kind of particulate filler material, wherein some particles of this particulate filler material present a single linear dimension greater than 10 μ m; And wherein this matrix material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material less than 15 volume percent.
In one the 3rd embodiment, the present invention relates to a kind of curtain coating composition, comprising:
A kind of carrier liq;
A kind of non-fluorinated polymer of non-fibrillation or fluoropolymer substrate material;
A kind of particulate filler material does not wherein have particle to present a single linear dimension greater than 10 μ m in this particulate filler material; And wherein this matrix material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material less than 15 volume percent.
In one the 4th embodiment, the present invention relates to a kind of curtain coating composition, comprising:
A kind of carrier liq;
A kind of non-fluorinated polymer of non-fibrillation or fluoropolymer substrate material;
A kind of particulate filler material, wherein some particles of this particulate filler material present a single linear dimension greater than 10 μ m; And wherein this matrix material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent.
In one the 5th embodiment, the present invention relates to a kind of curtain coating composition, comprising:
A kind of carrier liq;
A kind of non-fluorinated polymer of non-fibrillation or fluoropolymer substrate material;
A kind of particulate filler material, wherein some particles of this particulate filler material present a single linear dimension greater than 10 μ m; And wherein this matrix material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material less than 15 volume percent.
In one the 6th embodiment, the present invention relates to a kind of curtain coating composition, comprising:
A kind of carrier liq;
A kind of non-fluorinated polymer of non-fibrillation or fluoropolymer substrate material;
A kind of particulate filler material does not wherein have particle to present a single linear dimension greater than 10 μ m in this particulate filler material; And wherein this matrix material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent.
In one the 7th embodiment, the present invention relates to a kind of curtain coating composition, comprising:
A kind of carrier liq;
A kind of non-fluorinated polymer of non-fibrillation or fluoropolymer substrate material;
A kind of particulate filler material does not wherein have particle to present a single linear dimension greater than 10 μ m in this particulate filler material; And wherein this matrix material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material less than 15 volume percent.
Remove carrier and randomly after other additives of this discussion, promptly obtained film.These films can be the parts of multilayer film structure described here.
In one the 8th embodiment, the present invention relates to a kind of curtain coating composition, comprising:
A kind of carrier liq;
A kind of non-fluorinated polymer substrate material of non-fibrillation;
A kind of particulate filler material does not wherein have particle to present a single linear dimension greater than 10 μ m in this particulate filler material; And wherein this matrix material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent.
It should be understood that and one the 3rd can be placed on this second layer to form a kind of matrix material.In this second layer is wrapped in by first and the 3rd layer.But the 3rd layer of a kind of non-fluorinated polymer or fluoropolymer that can be same from a kind of curtain coating solution.
Therefore, the present invention the curtain coating composition also is provided, by the method for these preparation of compositions curtain coating multilayer film and the multilayer film that form by these compositions.These multilayer film comprise: first skin as described above, and this first skin comprises a kind of water-based or the castable polymkeric substance of solvent (as a kind of fluoropolymer); Place on this first layer one second internal layer as described above, this second layer comprises a kind of water-based or the castable polymkeric substance of solvent (for example a kind of fluoropolymer) or its mixture and a kind of particulate filler material, as described above; And placing on this second layer one the 3rd skin as described above, the 3rd skin comprises a kind of water-based or the castable polymkeric substance of solvent (for example a kind of fluoropolymer) or its mixture.
Typically, this first skin have from about 0.01 mil to about 0.7 mil, more particularly from about 0.02 mil to about 0.4 mil and the most especially from about 0.05 mil to the thickness of about 0.3 mil.
This second internal layer has from about 0.1 mil to about 0.8 mil generally, more particularly from about 0.2 mil to about 0.4 mil and the most especially from about 0.3 mil to the thickness of about 0.4 mil.
The 3rd skin for example has from about 0.01 mil to about 0.7 mil, the thickness from about 0.05 mil to about 0.3 mil more particularly from about 0.02 mil to about 0.4 mil and the most especially.
Follow-up layer (for example the 4th and layer 5) can have from about 0.01 mil to about 0.7 mil, the thickness from about 0.05 mil to about 0.3 mil more particularly from about 0.02 mil to about 0.4 mil and the most especially.
Phrase " multilayer " film is intended to comprise a plurality of layers that contact with each other of one or more films.Two layers of minimum existence, but three layers are special hope.Can in these multilayer film, comprise a plurality of additional layers, make these multilayer film can comprise 4,5,6 to 12 or the like layer.
Phrase " castable polymkeric substance " is intended to represent and can or otherwise be distributed in a kind of fluoropolymer or non-fluorinated polymer in a kind of liquid carrier medium by dispersion, dissolving, suspension, emulsification.This liquid carrier medium can be that water, organic solvent or this polymkeric substance may or otherwise be distributed in wherein any other liquid by dispersion, dissolving, suspension, emulsification.This liquid carrier medium can be a mixture of suitable liquid.In case be distributed in this mounting medium, this polymkeric substance and medium then can be deposited or curtain coating to a kind of propping material to form a kind of film.This or these polymkeric substance can mix with a kind of first carrier liq.This mixture can comprise a kind of dispersion of polymer beads in this first carrier liq, this polymkeric substance (or the monomer of this polymkeric substance or oligopolymer precursor) a kind of emulsion or this polymkeric substance a kind of solution in this first carrier liq of liquid droplets in this first carrier liq.
This or these castable polymkeric substance can also be to be distributed in a kind of monomer in a kind of carrier liq, this polymkeric substance or oligopolymer precursor.But more common curtain coating composition is emulsion or dispersion in aqueous medium.
The selection of this first carrier liq is based on concrete polymkeric substance and but this material waits to be introduced into residing form in the curtain coating composition of the present invention.If wish it is a kind of solution, a kind of solvent of then selecting this concrete fluoropolymer is as carrier liq.Suitable carriers for example comprises: DMAC, NMP, cellosolve or water and analogue.If wish it is a kind of dispersion, then suitable carriers is that this polymkeric substance is insoluble therein the sort of.For a kind of dispersion of polymer beads, a kind of aqueous solution will be a kind of suitable carrier liq.
But more common curtain coating composition is emulsion or dispersion in aqueous medium.Tensio-active agent can be used to prepare a kind of dispersion to the effective value of the surface tension that changes this carrier liq by one, so that this carrier liq can wetting these filling agent particles.Suitable surfactant compounds comprises ionogenic surfactant, amphoteric, cationic and non-ionic tensio-active agent.
In an exemplary embodiment, the mixture of a kind of polymkeric substance, a kind of carrier liq and a kind of dispersion of filling agent particle in a kind of second carrier liq merged form a kind of curtain coating composition.
General select fluoropolymer as outer so that chemical resistant properties, electrical insulating property, weathering resistance and/or stopping moisture are provided.
Phrase " fluoropolymer " is known in the art and for example is intended to comprise: polytetrafluoroethylene (PTFE), poly(vinylidene fluoride) (PVDF), polychlorotrifluoroethylene (PCTFE), fluorinated ethylene propylene (PVF), tetrafluoroethylene/hexafluoropropylene/ethylene copolymer (HTE), chlorotrifluoroethylene/vinylidene fluoride copolymer, chlorotrifluoroethylene/R 1216, ethene/chlorotrifluoroethylcopolymer copolymer (ECTFE), ethene/trifluoro-ethylene copolymer, Tefzel (ETFE), tetrafluoroethylene/propylene copolymer (TFE/P), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluor (alkyl vinyl ether) multipolymer (PFA, for example tetrafluoroethylene-perfluor (propyl vinyl ether)), poly(vinylidene fluoride), R 1216/tetrafluoroethylene/vinylidene multipolymer (being THV) and their mixture.
These fluoropolymers can be melt-processable, for example at poly(vinylidene fluoride); The multipolymer of vinylidene fluoride; The multipolymer of tetrafluoroethylene, hexafluoroethylene and vinylidene fluoride; The multipolymer of tetrafluoroethylene and hexafluoroethylene; And under the situation of the fluoroplastics of other melt-processable; Perhaps this fluoropolymer can not be a melt-processable, for example under the situation of the multipolymer of tetrafluoroethylene, TFE and low-level fluorinated vinyl ether and solidified fluoroelastomer.
The example of commercially available THV polymkeric substance comprises by Dyneon, those that LLC sells under following trade name: " DYNEON THV 2030G FLUOROTHERMOPLASTIC ", " DYNEON THV 220 FLUOROTHERMOPLASTIC ", " DYNEON THV 340C FLUOROTHERMOPLASTIC ", " DYNEON THV 415FLUOROTHERMOPLASTIC ", " DYNEON THV 500AFLUOROTHERMOPLA STIC ", " DYNEON THV 610GFLUOROTHERMOPLASTIC ", or " DYNEON THV 810G FLUOROTHERMOPLAS TIC ".
The example of commercially available HTE polymkeric substance for example comprises by Dyneon, those that LLC sells under following trade name: " DYNEON FLUOROTHERMOPLAS TIC HTE " (for example " DYNEON FLUOROTHERMOPLASTIC HTE X 1510 " or " DYNEON FLUOROTHERMOPLASTIC HTE X 1705 ").
The commercially available example that contains the fluoropolymer of vinylidene fluoride comprises that (for example) has those fluoropolymers of following trade name: as by Atofina, and Philadelphia, " KYNAR " (for example, " KYNAR 740 ") that Pa. sells; By Ausimont USA, Morristown, " HYLAR " (for example, " HYLAR 700 ") that N.J. sells; And by Dyneon, " FLUOREL " (for example, " FLUOREL FC-2178 ") that LLC sells.
The example of commercially available tetrafluoroethylene-perfluor (alkyl vinyl ether) multipolymer comprises that for example Solvay Solexis is with trade name " Hyflon PFA " or " Hyflon MFA "; And by E.I.diPont de Nemours﹠amp; Those that Company sells with " Teflon PFA ".
The example of commercially available vinyl fluoride fluoropolymer comprises the Nemours﹠amp by E.I.du Pont de; Company, Wilmington, the homopolymer of those vinyl fluorides that Del sells under trade name " TEDLAR ".
The example of commercially available (TFE/P) polymkeric substance comprises that by Dyneon LLC is under trade name " AFLAS " (for example " AFLAS TFE ELASTOMER FA 100H ", " AFLAS TFE ELASTOMER FA 150C ", " AFLAS TFE ELASTOMER FA 150L " or " AFLAS TFE ELASTOMER FA 150P ") or by E.I.du Pont de Nemours﹠amp; Company, Wilmington, those that Del sells under " VITON " (for example " VITON VTR-7480 " or " VITON VTR-7512 ").
The example of commercially available ETFE polymkeric substance for example comprises by Dyneon, those that LLC sells down at trade name " DYNEON FLUOROTHERMOPLASTIC ET 6210J ", " DYNEON FLUOROTHERMOPLASTIC ET 6235 " or " DYNEON FLUOROTHERMOPLASTIC ET 6240J ".
The example of commercially available ECTFE polymkeric substance comprises those that sell from Solvay Solexis Corp under trade name Halar 350 and Halar 500 resins.
Alternately, matrix material of the present invention can comprise a kind of thermoplasticity or the thermosetting polymer except that fluoropolymer.Suitable substituting matrix material comprises polyolefins and multipolymer thereof, as polyethylene kind, polypropylene-base, polyethylene, polymethylpentene and polyhutadiene, Resins, epoxy, resol, cyanate, polyester, polyamide-based, polycarbonate-based, polyimide, polyacrylic, polymethacrylic acid, the thermoplastic olefin class, ethylene-vinyl alcohol (EVOH), ethylene vinyl acetate (EVA), methacrylic acid ethyl (EMA), thermoplastic polyurethanes, thermoplastic silicone, the ionomer class, ethylene-propylene acid butyl ester (EBA), polyvinyl butyral acetal (PVB), propylene diene M class rubber (EPDM) or their mixture.
Particulate filler material of the present invention can comprise the microparticle material of any organic or inorganic.As used herein, term " particulate " and " particle " are intended to comprise fiber and thin slice.Suitable inorganic filler material comprises for example glass particle, ceramic particle, metallic particles, carbon granule and mineral grain.The suitable particle and the object lesson of thin slice comprise glass beads, glass microsphere, glass fibre, silica granule, carbon black, titanium dioxide granule, ferric oxide particles, aluminum particulate and barium titanate particles.Silica granule (particularly unbodied fused silica particles and the silica granule that makes by sol-gel method) and glass particle are applicable, the dielectric layer of stratiform circuit for example, and it requires a low specific inductivity.
The distribution of sizes of the shape of filling agent particle, the size of filling agent particle and filling agent particle can be an important parameters for characterizing particles filled composite article of the present invention.For example, scutellate pigment can cause the interference of light and other optical effects.This type of particle can comprise iron that mica applies or other metallic oxide complex things (for example from Wenzhou Pearlescent Pigments Co, Taizhu, the Taizhu TZ2013 purple of China; And from Merck KGaA, Darmstadt, the Xirallic T60-10WNT crystal silver of Germany).
In one embodiment of the invention, all particles of this particulate weighting agent all present the diameter less than about 10 microns (μ m).
In an alternate preferred embodiment of the present invention, each filling agent particle does not present the single linear dimension greater than about 10 μ m.
In another embodiment, the particle of this particulate weighting agent comprises some particles that present greater than the single linear dimension of 10 μ m.Presenting greater than the particle of the single linear dimension of 10 μ m can be from about 0.01% to about 50%, from about 0.1% to about 20% or from about 1% to about 10% of particle total amount with respect to the particulate per-cent that has less than the single linear dimension of 10 μ m.This linearity dimension can be to about 20 from about 11 μ m to about 50 μ m, from about 15 μ m.
As illustrated before, unexpectedly find, mix the particle that presents greater than the single linear dimension of 10 μ m and can help to provide unique characteristic final film.These characteristics comprise the tensile strength of increase, bigger opaqueness (with there not being comparing of larger particle) or the steam permeating rate that reduces.
Equally, this particle and need not be spheric.On the one hand, this particle can be rectangular, also is called " small pieces (platelet) " in this area.
In one aspect of the invention, each filling agent particle all is to be essentially spheric.
Of the present invention again on the other hand, the filling agent particle of this film has inconsistent size.The inconsistent particle of use size can provide a unexpected advantage of scattering of light and more homogeneous granules distribution is provided.Generally, the mean particle size that these particles have is between about 0.1 μ m and about 20 μ m, and wherein about 80% particle has the narrow particle size distribution between about 0.2 μ m and about 5 μ m.
Can handle with wet fastness, particles dispersed, matrix adhesivity or IR reflectivity, anti-UV that improves film and/or the mechanical characteristics of improving laminated film of the present invention this particulate filler material with a kind of surface treatment.For example, to some TiO 2Form is carried out passivation, otherwise they are photocatalytics.
To handle the useful suitable hydrophobic coating of particle of the present invention can comprise any heat-staple, present low surface energy and improved the coating material of the wet fastness of matrix material of the present invention.Suitable coating material comprises conventional silane coating, titanate coating and zirconate coating.
Matrix material of the present invention is mixed with a kind of first carrier liq.This mixture can comprise a kind of dispersion of polymer beads in this first carrier liq, this polymkeric substance (or the monomer of this polymkeric substance or oligopolymer precursor) a kind of dispersion (be a kind of emulsion) or this polymkeric substance a kind of solution in this first carrier liq of liquid droplets in this first carrier liq.
But residing form when waiting to be introduced in the curtain coating composition of the present invention that the selection of this first carrier liq is based on concrete matrix material and this matrix material.If wish it is a kind of solution, a kind of solvent of then selecting this concrete matrix material is as this carrier liq.Suitable carriers for example comprises: DMAC, NMP, cellosolve or water, and analogue.If wish it is a kind of dispersion, then suitable carriers is that this substrate material is insoluble therein the sort of.For a kind of dispersion of particles of fluoropolymer, a kind of aqueous solution will be a kind of suitable carrier liq.
The dispersion of particulate weighting agent of the present invention can be at this weighting agent in insoluble a kind of second suitable carrier liq wherein.
Tensio-active agent can be used to prepare a kind of dispersion to the effective value of the surface tension that changes this second carrier liq by one, so that this second carrier liq can wetting these filling agent particles.Suitable surfactant compounds comprises ionogenic surfactant, amphoteric, cationic and non-ionic tensio-active agent.
In an exemplary embodiment, the mixture of a kind of matrix material and first carrier liq and the dispersion of filling agent particle in a kind of second carrier liq merged form a kind of curtain coating composition.Generally, this curtain coating composition have about 10 and about 90 weight percents between (based on particle and polymeric matrix), from about 20 between about 70 weight percents or from about 25 to the solid between about 50 weight percents.
The viscosity of curtain coating composition of the present invention can be adjusted by adding suitable viscosity modifier.This type of properties-correcting agent comprises polyacrylic compounds, vegetable jelly and based on cellulosic compound.The object lesson of suitable viscosity modifier comprises polyacrylic acid, methylcellulose gum, polyoxyethylene, guar gum, tracasol, Xylo-Mucine, sodiun alginate and tragacanth.
Generally, this curtain coating composition have about 10 and about 90 weight percents between (based on particle and/or polymkeric substance), from about 20 between about 70 weight percents or from about 25 to the solid between about 50 weight percents.
In general, but this particulate filler material may be with from about 0% being present in the curtain coating polymer layer to about 60% scope by volume by volume.
On the one hand, this particulate weighting agent with based on the cumulative volume of these multilayer film for existing from about 2% to about 50% (for example from by volume about 8% to by volume about 25%).On the other hand, this particulate weighting agent with based on the cumulative volume of these multilayer film from by volume about 9% to by volume about 15% and exist.It should be understood that at this to comprise the subrange that falls in 0% to about 60% that being included as is the fractional scope.That is from about 0.5% to about 5.5%, from about 0.6% to about 10.3% etc.All scopes are all included at this.The digital scope that lists by end points comprises that all are comprised in numeral in this scope (for example 1 to 5, comprise 1,1.5,2,2.75,3,3.80,4,5, etc.).
The viscosity of curtain coating composition of the present invention can be adjusted by adding suitable viscosity modifier.This type of properties-correcting agent comprises polyacrylic compounds, vegetable jelly and based on cellulosic compound.The object lesson of suitable viscosity modifier comprises polyacrylic acid, methylcellulose gum, polyoxyethylene, guar gum, tracasol, Xylo-Mucine, sodiun alginate and tragacanth.
In order to prepare a kind of film, the method by routine (for example dip-coating, contrary roller coat cover, roll-type blade coating, board-like blade coating and gauge stick apply) is prolonged a laminar flow of said composition to a substrate.
Suitable substrate material comprises for example metallic film, polymeric film or ceramic membrane.The object lesson of suitable substrate comprises stainless steel paillon foil, Kapton or fluoropolymer film.
In a kind of exemplary casting method, as at U.S. Patent number 4,883, describe in detail in 716 (its content is combined in this in full with it), film is to have on the carrier band of low thermal mass by curtain coating to form.This carrier band is the part of a curtain coating utensil.This carrier band dipping passed be in a kind of fluoropolymer substrate material/particulate filler material dispersion in the dip pan at the bottom of the curtain coating column foot, thereby make a coating that on this carrier band, forms dispersion.The carrier band of this coating passes a metering zone then, and the metering scraper is removed excessive dispersion from the carrier band of this coating in this metering zone.After metering zone, the carrier band of this coating is sent into a drying zone, this drying zone is maintained under the temperature that is enough to carrier liq is removed from dispersion, thereby produces a kind of exsiccant film.The carrier band that will have dry film is then delivered to a baking/melting zone, and the temperature in this baking/melting zone is enough to make this to disperse intravital fluoropolymer and particulate is fixed or fusion.At last, make this carrier band pass a cooling plenum system, thus can with dip pan subsequently of this carrier tape guide with begin to form one with another layer of rear film, also or the stripping utensil that leads.This process can repeat desired many number of times, provides generally up to 7 layers, and 5 layers for example, wherein 3 are that fluoropolymer matrix/particulate filler material layer and 2 are the skins of one or more fluoropolymers.
In a kind of other exemplary casting method, the film of this coating can remain on this carrier substrate, the feasible a kind of unitized construction that forms substrate and cast film.The example of this situation can comprise fluoropolymer and a kind of polyimide, a kind of aluminium substrate or a kind of polycarbonate.In an other example, can between the curtain coating composition that is applied and this carrier band, introduce an independent substrate membrane, make that this castable fluoropolymer film is accumulated on this substrate.In an example, this substrate, Kapton, aluminum slice or a polycarbonate film can be supported on the carrier band and this curtain coating composition can be applied on this substrate.This curtain coating composition can be applied on two surfaces of this substrate thus, the suitable structure of thereby make this substrate is coated on end face and bottom surface. for example comprises: a kind of first castable fluoropolymer polymer/aluminium/a kind of second castable fluoropolymer polymer (it can be identical or different with this first castable fluoropolymer polymer) (for example PTFE/Al/PTFE), a kind of first castable fluoropolymer polymer/a kind of polyamide/a kind of second castable fluoropolymer polymer (it can be identical or different with this first castable fluoropolymer polymer) (FEP/ polyamide/FEP) for example, and a kind of first castable fluoropolymer polymer/a kind of Merlon/a kind of second castable fluoropolymer polymer (it can be identical or different with this first castable fluoropolymer polymer) (PVDF/ Merlon/PVDF) for example.
Other alternate substrate membranes can depend on for the desired technological temperature of fluoropolymer curtain coating composition that is deposited and adopt.Has the substrate that can use lesser temps than the fluoropolymer composition of low melting glass.
In an example, this carrier liq and processing aid (as tensio-active agent and/or viscosity modifier) are removed from this cast layer by evaporation and/or by thermolysis, so that a kind of film of this polymeric matrix and this particulate weighting agent to be provided.On the one hand, the polymeric matrix laminated film of particulate filling of the present invention is by preparing this cast film heating to evaporate this carrier liq.
The film of this matrix material and particulate weighting agent further can be heated to improve the physical property of this film.This can comprise the after fixing of this film.
On the one hand, these multilayer film have three layers.First skin is a kind of castable fluoropolymer, second internal layer be a kind of castable fluoropolymer together with a kind of particulate weighting agent described here, and the 3rd skin is a kind of castable fluoropolymer.On the other hand, one of this first and the 3rd skin or both can comprise from by volume about 0.01% to a kind of particulate weighting agent of about 12% by volume, and in particular by volume from about 0.01% to about 6%.
On the other hand, one the 4th can be placed on this first layer.The 4th layer is as a kind of castable fluoropolymer described here.Still on the other hand, a layer 5 can be placed on the 3rd layer.This layer 5 is as a kind of castable fluoropolymer described here.It is desirable to, the 4th and layer 5 be to be selected from: tetrafluoroethylene-perfluor (alkyl vinyl ether) is multipolymer or fluorizated ethylene propylene copolymer (FEP) or their mixture (PFA).In addition, the 4th and/or layer 5 can comprise the mixture of PTFE and a kind of PFA or FEP.
The 4th and layer 5 may further include as a kind of particulate weighting agent described here.One of the 4th and first skin or both can comprise from by volume about 0.01% to a kind of particulate weighting agent of about 12% by volume, and in particular by volume from about 0.01% to about 6%.
On the one hand, the skin of these multilayer film can be made by the cohesible fluoropolymer of a kind of melt.The cohesible material of suitable melt for example comprises: tetrafluoroethylene-perfluor (alkyl vinyl ether) multipolymer or fluorizated ethylene propylene copolymer (FEP) or their mixture.
Method of the present invention provides having of remaining to be produced economically to be lower than about 2 mils and even has been lower than the film of about 1 mil thickness.Film thickness is listed in this mode with " mil ", and one of them mil equals 0.001 inch.
Again aspect another, multilayer film of the present invention have about 0.6 mil to about 2 mils, more particularly from about 0.8 to the total thickness between about 1.5 mils.
In one embodiment, multilayer film of the present invention have dielectric breakdown strength (kV) greater than 3kV by ASTM method D3755 measurement.This dielectric breakdown strength particularly from greater than 3kV to about 12kV, from about 3kV about 7kV and extremely particularly from about 4kV about 6kV extremely.
Dielectric breakdown strength is to measure according to ASTM D3755 (being used for the dielectric breakdown voltage of solid electrically insulating material and the standard method of test of dielectric strength under DC voltage stress).
The specimen of 5 inches of 5 inches x is remained in two air dielectrics between the relative right cylinder, and these two cylindrical diameters are 2 inches, and length is 1 inch, and its edge is by the radius of sphering to 0.25 inch.By applying this sample is applied electric stress, until internal breakdown takes place with the cumulative volts DS of the uniform rate of 500V/s.Dielectric breakdown is to increase by the electric current in hook-up to finish generally, and this electric current increase may trigger a sensing member, as isolating switch or safety fuse.Trial voltage when record punctures.
In another embodiment, these multilayer film on the one side at least of film, have by ASTM method E424 measure greater than 70% solar reflectance.Solar reflectance on the one side at least of film is in particular from greater than 70% to about 99.9%, from about 75% to about 99% and particularly from about 80% to about 99%.
Solar reflectance is to measure according to ASTM E424 (being used for the solar energy transmission of sheeting and the standard method of test of reflectivity (land)).Be used for the data gathering of designated program requirement on 350 to 2100nm scopes of ASTM E424.Data summation from 400 to 1100nm is this program a kind of variant commonly used and is in this employed method.(only for 5820 example)
Used a kind of integration ball-type spectrophotometer to measure the spectral signature of this specimen (2 inches x 2 inches) on interested SPECTRAL REGION.Use smoke cured magnesium oxide (smoked magnesium oxide) as a standard that is used for reflecting fully with diffusing surface.Obtained with respect to the spectral-transmission favtor data of air and with respect to magnesian spectrum directional reflectance data.Solar energy transmission and the reflectivity represented with per-cent obtain by the spectrographic reflectivity is carried out integration on standard sun power distributes.Solar energy transmission be pass this measured thin film and reflectivity is with respect to a planar survey of this film generally.Opaqueness (%) is defined as 100%-transmittance %.
In another embodiment again, these multilayer film have by ASTM method F1249 measure less than about 20g/m 2The steam permeating rate in/sky.Steam permeating rate is especially less than about 16g/m 2/ day, more particularly less than about 13g/m 2/ day and the most especially less than about 8g/m 2/ day.
Steam permeating rate is to measure according to ASTM F1249 (using a kind of synthetic infrared sensor to pass the steam permeating rate of plastics film and sheet material).
Use lubricating grease and O shape ring that the specimen of 4 inches of 4 inches x is sealed tightly between a dried chamber and moist chamber.The water vapour that diffuses through this film and nitrogen mix and are carried to the infrared sensor of a pressure modulation in doing the chamber.The part of the infrared energy that this sensor measurement water vapour is absorbed and produce an electrical signal, the amplitude of this electrical signal and the concentration of water vapour are proportional.The amplitude of this electrical signal is compared with a kind of amplitude of calibrating film with known water transmission rates, calculate the speed that moisture sees through this testing film thus.This test is carried out under constant temp or humidity, for example under 39 ℃ and 100% relative humidity.In another embodiment, these multilayer film have by ASTM method E424 measure greater than about 80% light obscuration.This light obscuration especially greater than about 80, more particularly greater than about 85 and the most especially greater than about 95.
In a specific embodiment, when these multilayer film have thickness between about 0.7 mil and about 2 mils, these multilayer film described here have the dielectric breakdown strength greater than 3kV (kV) measured by ASTM method D3755, by ASTM method E424 measure greater than 70% solar reflectance, by ASTM method F1249 measure less than 20g/m 2The steam permeating rate in/sky.
In another embodiment, these multilayer film have the characteristic on two sides.For example, they may have the surface of a dead color simultaneously having a surface white, highly reflective at another side.In another example, they may have a surface white, highly reflective and have dark, a non-reflexive surface at another side in one side.In another embodiment, they may have a surface white, highly reflective and have dark, a reflexive surface at another side in one side.
Color on arbitrary of this film can be by using a kind of CIE of being called L *a *b *The standard method of color appearance models is measured and is represented.In a specific embodiments of the film of a kind of two sides color, a black side and a white face may be given prominence to.A low L *Value indicates a kind of more black color, wherein L *The=0th, the most extreme black level value.A high L *Value indicates a kind of whiter color, wherein L *The=100th, the white observed value of maximum diffusion.
The outer field fluoropolymer that specifically is used for multilayer film described here is unique material, because they show a series of outstanding characteristics, for example high-clarity, good dielectric strength, high purity, unreactiveness, low-friction coefficient, high thermostability, excellent weathering resistance and anti-UV.Fluoropolymer is used in often and requires in the high performance application, wherein requires the combination of above characteristic often.Yet because their low surface energy, fluoropolymer is difficult to by great majority (if not all words) non-fluorinated polymer materials (liquid also or solid) wetting.
Subsequently, a FAQs running into of fluoropolymer is to be difficult to be adhered on the surface of non-fluorinated polymer.Once more, this problem is not that the fluoropolymer laminated composite material of fluoropolymer is challenging especially at least one layer wherein.
The method that the invention provides novel multilayer film and prepare these multilayer film by the surface treatment of using suitable material to carry out further choosing wantonly subsequently in conjunction with a plurality of layers multiple deposition.In general, multilayer film of the present invention comprise the outer of a fluoropolymer that comprises modification and the internal layer one or more described here with polymeric matrix/one or more particle films.
Term " fluoropolymer of modification " is intended to comprise the fluoropolymer body modification or surface modification or that both all have.The modification of body fluoropolymer comprise with comprised be grafted within this fluoropolymer main chain or on polar functionality be included in.The fluoropolymer material of such modification can be used in combination or be used as basic fluoroplymer layer with a unmodified fluoroplymer layer and a non-fluorinated polymer layer.For example, maleic anhydride modified ETFE is suitable for nylon is adhered on the untreated ETFE substrate.
The surface modification of fluoropolymer provides a kind of another kind of mode of fluoropolymer of useful in the present invention modification.Generally, the polar functionality is attached on this fluoropolymer surface, thereby makes it to be easier to wetting and offer an opportunity for Chemical bond.Exist to make a several method that fluoropolymer is surface-functionalized, comprise chemical milling, physics-mechanical etching, plasma etching, corona treatment, chemical vapour deposition or their arbitrary combination.In one embodiment, this chemical milling comprises sodium ammonia (sodium ammonia) or sodium naphthalene (sodium naphthalene).The air abrasion that a kind of exemplary physics-mechanical etching can comprise sandblast and use silica.In another embodiment, plasma etching comprises reactive plasma, for example the mixture of hydrogen, oxygen, acetylene, methane and they and nitrogen, argon gas and helium.The steam that corona treatment can comprise reactive hydrocarbon is for example: ketone (for example acetone), alcohols, to chloro-styrene, vinyl cyanide, propylene diamine, anhydrous ammonia, styrene sulfonic acid, tetracol phenixin, tetren, hexahydroaniline, titanium isopropylate, decyl amine, tetrahydrofuran (THF), diethyl triamine, TERTIARY BUTYL AMINE, quadrol, Toluene-2,4-diisocyanate, the 4-vulcabond, glycidyl methacrylate, the triethyl tetramine, hexane, triethylamine, methyl alcohol, vinyl-acetic ester, isopropyl methyl amine, vinyl butyl ether, methyl methacrylate, the 2-vinyl pyrrolidone, methyl vinyl ketone, dimethylbenzene or their mixture.
Some technology have been used and have been comprised one of them the combination of a plurality of steps of these methods.For example, surface active can be finished by plasma body in the presence of a kind of gaseous species that is stimulated or corona.For example, surface active can be finished by carry out corona treatment in the presence of a kind of solvent gas (as acetone).
Do not accept opinion and limit, find that this method provides at a kind of fluoropolymer of modification and the strong ply adhesion between a kind of non-fluorinated polymer interface (or fluoropolymer of a kind of second modification).In a kind of mode, the shaping thing of fluoropolymer and non-fluorinated polymer is to form separately separately.Subsequently, this fluoropolymer shaping thing is passed through at United States Patent (USP) 3030290,3255099,3274089,3274090,3274091,3275540,3284331,3291712,3296011,3391314,3397132,3485734,3507763,3676181,4549921 and 6,726, the treatment process of describing in 979 is advanced surface treatment, and the content of teaching of these patents is combined in this with it by reference in full for all purposes.Then, the fluoropolymer of the modification that produces and the shaping thing of non-fluorinated polymer are contacted (for example passing through heat lamination) together to form a kind of multilayer film.At last, can use the wavelength in UVA, UVB and/or UVC scope to carry out the UV radiation these multilayer film.
On the one hand, use corona discharge to handle on the surface of this fluoropolymer substrate, wherein with electrode region acetone, tetrahydrofuran (THF), methyl ethyl ketone, ethyl acetate, isopropyl acetate or the submergence of propyl acetate steam.
Corona discharge is that the electric capacity exchange by the gaseous medium that exists between the electrode at two intervals produces, and wherein at least one electrode insulate by a dielectric barrier layer and with this gaseous medium.Corona discharge is limited to alternating-current to a certain extent because of its capacitive properties on the source.It is a kind of high voltage low current phenomenon, and wherein voltage is typically typically measured with milliampere with kilovoltage measurement and electric current.Corona discharge can be kept on wide pressure and range of frequency.Limit and normal atmosphere that from 0.2 to 10 atmospheric pressure defines the corona discharge operation generally are preferred generally.Use range is from the frequency of 20Hz to 100MHz suitably: especially, scope is from 500Hz, especially 3000Hz to 10MHz.
When using dielectric barrier layer that the electrode at two intervals is insulated with this gaseous medium separately, this corona discharge phenomenon is called as electrodeless discharge often, and when when using a single dielectric barrier layer one of them electrode being insulated with this gaseous medium, the corona discharge of generation is called as half corona discharge often.It is to be used for representing two types corona discharge that term " corona discharge " runs through this specification sheets, that is: electrodeless discharge and half corona discharge.
All details that relate to the Corona discharge Treatment program are transferring E.I.du Pont de Nemours and Company, provide in a series of United States Patent (USP)s of USA, and be described in the U.S. Patent number 3 of expiration, 676, in 181 and the U.S. Patent number 6 of Saint-Gobain Performance Plastics Corporation, in 726,979, their content of teaching is combined in this in full with it by reference for all purposes.An example of the technology that is proposed can find among 181 (Kowalski) at U.S. Patent number 3,676.The atmosphere that is used for closed treatment facility is at 20% acetone (by volume) of nitrogen and is successive.For example, make a kind of multilayer film of constant feed or the skin of the film that particulate is filled stand the watt hr of every square feet of film/slice surfaces between 0.15 and 2.5.This fluoropolymer can be handled to increase bonding on this film/shaping thing two-sided.Store on this material can being placed in the isolation liner of a non-silication then.Material after C-handles continued do not have significant surperficial wetting properties, agglutinating value(of coal) and fusible loss more than 1 year.
On the other hand, use plasma body to handle on the surface of this fluoropolymer substrate.Term " chemical vapour deposition of plasma body enhanced " be known (PECVD) in this area and be meant a kind of with film from gaseous state (steam) to solid deposited to an on-chip method.Relate to some chemical reactions in this process, these plasma generation that are reflected at reactant gases take place afterwards.This plasma body is by the DC discharge generation between RF (AC) frequency or two electrodes generally, has wherein placed this substrate between these electrodes and this space has been full of reactant gases.Plasma body is that wherein significantly thereby the atom of per-cent or molecule are ionized and produce reactive ion, electronics, group and any gas of UV radiating.
In another exemplary, at least one major surfaces of this fluoroplymer layer comprises colloid silica.This colloid silica is typically to provide a fusible amount to be present in a kind of solution between this first layer and the second layer.In one embodiment, this colloid silica is present in a kind of a kind of solution of the adhesion characteristic that does not influence this colloid silica nocuously.In an example, this solution can be water-based.A kind of commercially available colloid silica solution is conduct Available.In one embodiment, except that this colloid silica solution, can use a kind of binding soln.Be susceptible to any known binding soln compatible with colloid silica.For example, can use a kind of associativity fluoropolymer, as FEP or PFA.Typically, this binding soln and colloid silica are to apply with the ratio at least about 25/75 by weight, as by weight about 40/60, as by weight about 50/50 or even about by weight 75/25.
Multilayer film of the present invention can be used for protecting (particularly) electronic unit to avoid moisture, weather, heat, radiation, physical hazard and/or make this parts insulation.Be used to protect the example of optoelectronic component to include but not limited to: packing is based on the photovoltaic module of crystalline silicon, based on the thin photovoltaic module of amorphous silicon, CIGS, DSC, OPV or CdTe, OLED; LED; LCD, printed circuit board (PCB), flexible display and printed-wiring board (PWB).
Any one can contain common additive preparation in the disclosed layer, comprising: antioxidant, UV blocking agent, UV stablizer, hindered amine stabilizer, fixing agent, linking agent, additional pigment, processing aid and analogue.
Below from 1 to 48 paragraph of sequentially enumerating a plurality of different aspect of the present invention is provided.In one embodiment, in first section (1), the invention provides a kind of curtain coating composition, said composition comprises: a kind of carrier liq; A kind of fluoropolymer substrate material of non-fibrillation; A kind of particulate filler material, be selected from: the compound of silica microparticle, glass beads, glass microsphere, glass fibre, titanium dioxide granule, barium titanate particles, lime carbonate, zinc oxide, mica, clay, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, aluminic acid cobalt blue, sulphur sodium silicoaluminate, magnesium hydroxide, antimonous oxide, organophosphate, bromination or its mixture, wherein some particles of this particulate weighting agent present a single linear dimension greater than 10 μ m; And wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent.
2. a curtain coating composition comprises: a kind of carrier liq; A kind of fluoropolymer substrate material of non-fibrillation; A kind of particulate filler material, be selected from: the compound of silica microparticle, glass beads, glass microsphere, glass fibre, titanium dioxide granule, barium titanate particles, lime carbonate, zinc oxide, mica, clay, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, aluminic acid cobalt blue, sulphur sodium silicoaluminate, magnesium hydroxide, antimonous oxide, organophosphate, bromination or its mixture, wherein some particles of this particulate weighting agent present a single linear dimension greater than 10 μ m; And wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material less than 15 volume percent.
3. a curtain coating composition comprises: a kind of carrier liq; A kind of fluoropolymer substrate material of non-fibrillation; A kind of particulate filler material, be selected from: the compound of silica microparticle, glass beads, glass microsphere, glass fibre, titanium dioxide granule, barium titanate particles, lime carbonate, zinc oxide, mica, clay, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, aluminic acid cobalt blue, sulphur sodium silicoaluminate, magnesium hydroxide, antimonous oxide, organophosphate, bromination or its mixture wherein do not have particle to present a single linear dimension greater than 10 μ m in this particulate weighting agent; And wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material less than 15 volume percent.
4. a curtain coating composition comprises: a kind of carrier liq; A kind of fluoropolymer substrate material of non-fibrillation; A kind of particulate filler material, be selected from: the compound of lime carbonate, zinc oxide, mica, clay, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, aluminic acid cobalt blue, sulphur sodium silicoaluminate, magnesium hydroxide, antimonous oxide, organophosphate, bromination or its mixture, wherein some particles of this particulate weighting agent present a single linear dimension greater than 10 μ m; And wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent.
5. a curtain coating composition comprises: a kind of carrier liq; A kind of fluoropolymer substrate material of non-fibrillation; A kind of particulate filler material, be selected from: the compound of lime carbonate, zinc oxide, mica, clay, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, aluminic acid cobalt blue, sulphur sodium silicoaluminate, magnesium hydroxide, antimonous oxide, organophosphate, bromination or its mixture, wherein some particles of this particulate weighting agent present a single linear dimension greater than 10 μ m; And wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material less than 15 volume percent.
6. a curtain coating composition comprises: a kind of carrier liq; A kind of fluoropolymer substrate material of non-fibrillation; A kind of particulate filler material, be selected from: the compound of lime carbonate, zinc oxide, mica, clay, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, aluminic acid cobalt blue, sulphur sodium silicoaluminate, magnesium hydroxide, antimonous oxide, organophosphate, bromination or its mixture wherein do not have particle to present a single linear dimension greater than 10 μ m in this particulate weighting agent; And wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent.
7. a curtain coating composition comprises: a kind of carrier liq; A kind of fluoropolymer substrate material of non-fibrillation; A kind of particulate filler material, be selected from: the compound of lime carbonate, zinc oxide, mica, clay, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, aluminic acid cobalt blue, sulphur sodium silicoaluminate, magnesium hydroxide, antimonous oxide, organophosphate, bromination or its mixture wherein do not have particle to present a single linear dimension greater than 10 μ m in this particulate weighting agent; And wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material less than 15 volume percent.
8. as each described curtain coating composition in the paragraph 1 to 7, wherein this curtain coating composition has at room temperature at about 10cp to about 100, the viscosity between the 000cp.
9. as each described curtain coating composition in the paragraph 1 to 8, wherein: this curtain coating composition comprises a kind of the be divided into prose style free from parallelism of particle in this carrier liq of particle and this filler material of this fluoropolymer.
10. as each described curtain coating composition in the paragraph 1 to 8, wherein this carrier liq comprises water.
11. as each described curtain coating composition in the paragraph 1 to 10, wherein this fluoropolymer is to be selected from: tetrafluoroethylene, poly(vinylidene fluoride), polychlorotrifluoroethylene, fluorinated ethylene propylene, tetrafluoroethylene/hexafluoropropylene/ethylene copolymer, chlorotrifluoroethylene/vinylidene fluoride copolymer, chlorotrifluoroethylene/R 1216, chlorotrifluoroethylene/ethylene copolymer, ethene/trifluoro-ethylene copolymer, Tefzel, fluorizated ethylene/propene copolymer or their mixture.
12. as each described curtain coating composition in the paragraph 1 to 11, wherein these filling agent particles comprise the inorganic filler particle of coating, the inorganic filler particle of these coatings comprises an inorganic core and centers on a coat of this core.
13. as paragraph 12 described curtain coating compositions, wherein this coat is a silane coating, zirconate coating or titanate coating.
14. as each described curtain coating composition in paragraph 3,6 and 7, wherein these filling agent particles have the biggest ball equivalent diameter less than about 10 μ m.
15. as each described curtain coating composition in the paragraph 1 to 14, wherein each filling agent particle all is a spheric.
16. as each described curtain coating composition in the paragraph 1 to 15, wherein all filling agent particles all have identical in fact granularity.
17. as each described curtain coating composition in the paragraph 1 to 16, further comprise a kind of tensio-active agent, thereby this tensio-active agent is the surface tension that is used to change this liquid makes wetting these filling agent particles of this liquid.
18. as paragraph 17 described curtain coating compositions, wherein this tensio-active agent is a kind of ionic surface active agent or a kind of nonionogenic tenside.
19. as paragraph 17 described curtain coating compositions, wherein this tensio-active agent is a kind of amphoteric or cationic tensio-active agent.
20. as each described curtain coating composition in the paragraph 1 to 19, further comprise: a kind of viscosity modifier, thereby this viscosity modifier is added into the viscosity of adjusting this curtain coating composition and postpones separating of this particulate weighting agent and composition, so that a kind of stable, curtain coating composition uniformly is provided.
21. a film comprises: a kind of fluoropolymer substrate material of non-fibrillation; A kind of particulate filler material, be selected from: the compound of silica microparticle, glass beads, glass microsphere, glass fibre, titanium dioxide granule, barium titanate particles, lime carbonate, zinc oxide, mica, clay, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, aluminic acid cobalt blue, sulphur sodium silicoaluminate, magnesium hydroxide, antimonous oxide, organophosphate, bromination or its mixture, wherein some particles of this particulate weighting agent present a single linear dimension greater than 10 μ m; And wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent.
22. a film comprises: a kind of fluoropolymer substrate material of non-fibrillation; A kind of particulate filler material, be selected from: the compound of silica microparticle, glass beads, glass microsphere, glass fibre, titanium dioxide granule, barium titanate particles, lime carbonate, zinc oxide, mica, clay, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, aluminic acid cobalt blue, sulphur sodium silicoaluminate, magnesium hydroxide, antimonous oxide, organophosphate, bromination or its mixture, wherein some particles of this particulate weighting agent present a single linear dimension greater than 10 μ m; And wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material less than 15 volume percent.
23. a film comprises: a kind of fluoropolymer substrate material of non-fibrillation; A kind of particulate filler material, be selected from: the compound of silica microparticle, glass beads, glass microsphere, glass fibre, titanium dioxide granule, barium titanate particles, lime carbonate, zinc oxide, mica, clay, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, aluminic acid cobalt blue, sulphur sodium silicoaluminate, magnesium hydroxide, antimonous oxide, organophosphate, bromination or its mixture wherein do not have particle to present a single linear dimension greater than 10 μ m in this particulate weighting agent; And wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material less than 15 volume percent.
24. a film comprises: a kind of fluoropolymer substrate material of non-fibrillation; A kind of particulate filler material, be selected from: the compound of lime carbonate, zinc oxide, mica, clay, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, aluminic acid cobalt blue, sulphur sodium silicoaluminate, magnesium hydroxide, antimonous oxide, organophosphate, bromination or its mixture, wherein some particles of this particulate weighting agent present a single linear dimension greater than 10 μ m; And wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent.
25. a film comprises: a kind of fluoropolymer substrate material of non-fibrillation; A kind of particulate filler material, be selected from: the compound of lime carbonate, zinc oxide, mica, clay, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, aluminic acid cobalt blue, sulphur sodium silicoaluminate, magnesium hydroxide, antimonous oxide, organophosphate, bromination or its mixture, wherein some particles of this particulate weighting agent present a single linear dimension greater than 10 μ m; And wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material less than 15 volume percent.
26. a film comprises: a kind of fluoropolymer substrate material of non-fibrillation; A kind of particulate filler material, be selected from: the compound of lime carbonate, zinc oxide, mica, clay, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, aluminic acid cobalt blue, sulphur sodium silicoaluminate, magnesium hydroxide, antimonous oxide, organophosphate, bromination or its mixture wherein do not have particle to present a single linear dimension greater than 10 μ m in this particulate weighting agent; And wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent.
27. a film comprises: a kind of fluoropolymer substrate material of non-fibrillation; A kind of particulate filler material, be selected from: the compound of lime carbonate, zinc oxide, mica, clay, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, aluminic acid cobalt blue, sulphur sodium silicoaluminate, magnesium hydroxide, antimonous oxide, organophosphate, bromination or its mixture wherein do not have particle to present a single linear dimension greater than 10 μ m in this particulate weighting agent; And wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material less than 15 volume percent.
28. as each described film in the paragraph 21 to 27, wherein this fluoropolymer is to be selected from: tetrafluoroethylene, poly(vinylidene fluoride), polychlorotrifluoroethylene, fluorinated ethylene propylene, tetrafluoroethylene/hexafluoropropylene/ethylene copolymer, chlorotrifluoroethylene/vinylidene fluoride copolymer, chlorotrifluoroethylene/R 1216, chlorotrifluoroethylene/ethylene copolymer, ethene/trifluoro-ethylene copolymer, Tefzel, fluorizated ethylene/propene copolymer or their mixture.
29. as each described film in the paragraph 21 to 28, wherein these filling agent particles comprise the inorganic filler particle of coating, the inorganic filler particle of these coatings comprises an inorganic core and centers on a coat of this core.
30. as paragraph 29 described films, wherein this coat is a silane coating, zirconate coating or titanate coating.
31. as each described film in paragraph 23,26 and 27, wherein these filling agent particles have the biggest ball equivalent diameter less than about 10 μ m.
32. as each described film in the paragraph 21 to 31, wherein each filling agent particle all is a spheric.
33. as each described film in the paragraph 21 to 34, wherein all filling agent particles all have identical in fact granularity.
34. multilayer film comprise: one first fluoropolymer film; One as each described film in the paragraph 21 to 33 or a film that comprises and the following: a kind of fluoropolymer substrate material of non-fibrillation; And particulate filler material, be selected from: the compound of silica microparticle, glass beads, glass microsphere, glass fibre, titanium dioxide granule, barium titanate particles, lime carbonate, zinc oxide, mica, clay, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, aluminic acid cobalt blue, sulphur sodium silicoaluminate, magnesium hydroxide, antimonous oxide, organophosphate, bromination or its mixture wherein do not have particle to present a single linear dimension greater than 10 μ m in this particulate weighting agent; Wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent; And one second fluoropolymer film.
35. multilayer film comprise: one as each described the first film in the paragraph 21 to 33 or a film that comprises and the following: a kind of fluoropolymer substrate material of non-fibrillation; And particulate filler material, be selected from: the compound of silica microparticle, glass beads, glass microsphere, glass fibre, titanium dioxide granule, barium titanate particles, lime carbonate, zinc oxide, mica, clay, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, aluminic acid cobalt blue, sulphur sodium silicoaluminate, magnesium hydroxide, antimonous oxide, organophosphate, bromination or its mixture wherein do not have particle to present a single linear dimension greater than 10 μ m in this particulate weighting agent; Wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition, this laminated film comprises greater than the filler material of 15 volume percent, comprises the filler material of one first per-cent; And one as each described second film or a film that comprises and the following in the paragraph 21 to 33: a kind of fluoropolymer substrate material of non-fibrillation; And particulate filler material, be selected from: silica microparticle, glass beads, glass microsphere, glass fibre, titanium dioxide granule, barium titanate particles or its mixture wherein do not have particle to present a single linear dimension greater than 10 μ m in this particulate weighting agent; Wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition, this laminated film comprises greater than the filler material of 15 volume percent, comprises the filler material of one second per-cent.
36., comprising as paragraph 35 described multilayer film: as each described film in the paragraph 21 to 33 or one or more extra plays that comprise the film of and the following: a kind of fluoropolymer substrate material of non-fibrillation; And particulate filler material, be selected from: the compound of silica microparticle, glass beads, glass microsphere, glass fibre, titanium dioxide granule, barium titanate particles, lime carbonate, zinc oxide, mica, clay, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, aluminic acid cobalt blue, sulphur sodium silicoaluminate, magnesium hydroxide, antimonous oxide, organophosphate, bromination or its mixture wherein do not have particle to present a single linear dimension greater than 10 μ m in this particulate weighting agent; Wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent, and wherein the per-cent of filler material can be identical or different.
37., further comprise a fluoropolymer skin as the described multilayer film in one of paragraph 35 or 36.
38. as each described multilayer film in the paragraph 34 to 36, wherein this or these fluoroplymer layer (if the words that exist) is selected from PTFE, FEP or PFA independently of one another.
39. a photovoltaic device comprises: photovoltaic component and as paragraph 22 to 38 described any films, wherein this photovoltaic component and film are encapsulated in together.
40. a method for preparing multilayer film may further comprise the steps: a kind of curtain coating composition is coated on a kind of matrix, and this curtain coating composition comprises: a kind of carrier; A kind of fluoropolymer substrate material of non-fibrillation; A kind of particulate filler material, be selected from: the compound of silica microparticle, glass beads, glass microsphere, glass fibre, titanium dioxide granule, barium titanate particles, lime carbonate, zinc oxide, mica, clay, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, aluminic acid cobalt blue, sulphur sodium silicoaluminate, magnesium hydroxide, antimonous oxide, organophosphate, bromination or its mixture, wherein some particles of this particulate weighting agent present the single linear dimension of about 10 μ m; And wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition; This laminated film is contacted with a kind of second curtain coating composition, and wherein this second curtain coating composition comprises: a kind of carrier; And polymer materials, a kind of multilayer film is provided thus; And further these multilayer film are contacted with a kind of the 3rd curtain coating composition, wherein the 3rd curtain coating composition comprises: a kind of carrier; And polymer materials, a kind of 3 layers multilayer film are provided thus, wherein this granular layer is between this first and the 3rd layer.
41. as paragraph 40 described methods, further comprise a step that applies this laminated film with one or more curtain coating compositions, this curtain coating composition comprises: a kind of carrier; A kind of fluoropolymer substrate material of non-fibrillation; A kind of particulate filler material, be selected from: the compound of silica microparticle, glass beads, glass microsphere, glass fibre, titanium dioxide granule, barium titanate particles, lime carbonate, zinc oxide, mica, clay, talcum, ferric oxide, carbon black, zinc sulphide, barium sulfate, zinc sulfite, aluminic acid cobalt blue, sulphur sodium silicoaluminate, magnesium hydroxide, antimonous oxide, organophosphate, bromination or its mixture, wherein some particles of this particulate weighting agent present the single linear dimension of about 10 μ m; And wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of multi-layer compound film layer effectively relative value be included in the said composition.
42., comprise further this multi-layer compound film is contacted with a kind of curtain coating composition that wherein this curtain coating composition comprises: a kind of carrier as paragraph 41 described methods; And polymer materials, provide thus to have one first outer field a kind of multilayer film.
43., comprise further this multi-layer compound film is further contacted with a kind of curtain coating composition that wherein this curtain coating composition comprises: a kind of carrier as paragraph 42 described methods; And a kind of polymer materials, provide thus to have one second outer field a kind of multilayer film, wherein these MULTILAYER COMPOSITE granular layers are between these two skins.
44., further may further comprise the steps: make a skin stand a charged particle technology as each described method in paragraph 40,42 or 43.
45. as paragraph 44 described methods, wherein this charged particle technology is corona discharge or Cement Composite Treated by Plasma.
46. as paragraph 45 described methods, wherein this corona treatment is to carry out in the presence of a kind of solvent atmosphere.
47. as paragraph 46 described methods, wherein this solvent atmosphere is a kind of ketone.
48. as paragraph 39 described photovoltaic devices, wherein these multilayer film are liners behind of this photovoltaic component.
Below from 1 to 68 paragraph of sequentially enumerating a plurality of other aspect of the present invention is provided.In one embodiment, in first section (1), the invention provides a kind of multilayer film, these multilayer film comprise: a first layer that comprises a kind of water-based or the castable fluoropolymer of solvent; Place a second layer on this first layer, this second layer comprises a kind of water-based or the castable fluoropolymer of solvent or its mixture and a kind of particulate filler material or its mixture, and wherein this particulate filler material is with from about 10% being present in this castable fluoropolymer to about 45% scope by volume by volume; And place on this second layer one the 3rd layer, the 3rd layer comprises a kind of water-based or castable fluoropolymer of solvent or mixture.
2. as paragraph 1 described multilayer film, wherein this particulate weighting agent with based on the cumulative volume of these multilayer film from by volume about 8% to by volume about 25% and exist.
3. as the described multilayer film in one of paragraph 1 or 2, wherein this particulate weighting agent with based on the cumulative volume of these multilayer film from by volume about 9% to by volume about 15% and exist.
4. as each described multilayer film in the paragraph 1 to 3, wherein this first layer further comprises from by volume about 0.0% to a kind of particulate weighting agent of about 12% by volume.
5. as paragraph 4 described multilayer film, wherein the particulate weighting agent of this first layer is from by volume about 0.0% to by volume about 6% and exist.
6. as each described multilayer film in the paragraph 1 to 5, wherein the 3rd layer further comprises from by volume about 0.0% to a kind of particulate weighting agent of about 12% by volume.
7. as paragraph 6 described multilayer film, wherein this trilaminar particulate weighting agent is from by volume about 0.0% to by volume about 6% and exist.
8. as each described multilayer film in the paragraph 4 to 7, wherein this particulate weighting agent can be one or more weighting agents.
9. as each described multilayer film in the paragraph 1 to 8, further comprise one the 4th layer that is placed on this first layer, the 4th layer comprises a kind of water-based or the castable fluoropolymer of solvent or its mixture.
10. as paragraph 9 described multilayer film, further comprise a layer 5 that places on the 3rd layer, this layer 5 comprises a kind of water-based or the castable fluoropolymer of solvent or its mixture.
11. as the described multilayer film in one of paragraph 9 or 10, wherein the 4th and layer 5 be to be selected from: tetrafluoroethylene-perfluor (alkyl vinyl ether) multipolymer (PFA) or fluorizated ethylene propylene copolymer (FEP) or their mixture.
12. as each described multilayer film in the paragraph 9 to 11, wherein the 4th or layer 5 further comprise from by volume about 0.0% to a kind of particulate weighting agent of about 12% by volume.
13. as paragraph 12 described multilayer film, wherein the 4th or the particulate weighting agent of layer 5 be from by volume about 0.0% to by volume about 6% and exist.
14. as each described multilayer film in the paragraph 1 to 13, wherein these multilayer film have in about 0.7 mil to the thickness between about 2 mils.
15. as paragraph 14 described multilayer film, wherein these multilayer film have the thickness between about 0.8 mil and about 1.5 mils.
16. as each described multilayer film in the paragraph 1 to 5, wherein this dielectric breakdown strength (kV) is measured as greater than 3kV by ASTM method D3755.
17. as each described multilayer film in the paragraph 1 to 16, wherein this solar reflectance is measured as greater than 70% by ASTM method E424.
18. as each described multilayer film in the paragraph 1 to 17, wherein this steam permeating rate is measured as less than about 20g/m by ASTM method F1249 2/ day.
19. as each described multilayer film in the paragraph 1 to 18, wherein this light obscuration is measured as greater than about 80% by ASTM method E424.
20. as each described multilayer film in the paragraph 1 to 19, wherein when these multilayer film have thickness between about 0.7 mil and about 2 mils, this dielectric breakdown strength (kV) is measured as greater than 3kV by ASTM method D3755, this solar reflectance is measured as greater than 70% by ASTM method E424, and this steam permeating rate is measured as less than 20g/m by ASTM method F1249 2/ day.
21. be used to prepare a kind of curtain coating composition series of multilayer film, this curtain coating composition series comprises: but but a kind of first curtain coating composition of a kind of first carrier liq and a kind of first curtain coating fluoropolymer comprised; But but comprise a kind of second curtain coating composition of a kind of second carrier liq, a kind of second curtain coating fluoropolymer and a kind of particulate filler material, but wherein this particulate filler material with from about 20% being present in this second curtain coating fluoropolymer by volume to about 45% scope by volume; But but and a kind of the 3rd curtain coating composition that comprises a kind of the 3rd carrier liq and the 3rd curtain coating fluoropolymer.
22. as paragraph 21 described curtain coating composition series, wherein this first, second and the 3rd carrier liq be water-based, be a kind of solvent or its mixture.
23. as one of paragraph 21 or 22 described curtain coating composition series, wherein this particulate weighting agent be with based on the cumulative volume of these multilayer film from by volume about 8% to by volume about 25% and exist.
24. as each described curtain coating composition series in the paragraph 21 to 23, wherein this particulate weighting agent be with based on the cumulative volume of these multilayer film from by volume about 9% to by volume about 15% and exist.
25. as each described curtain coating composition series in the paragraph 21 to 24, but wherein this first curtain coating composition further comprises from by volume about 0.0% to a kind of particulate weighting agent of about 12% by volume.
26. as paragraph 25 described curtain coating composition series, wherein the particulate weighting agent of this first layer is from by volume about 0.0% to by volume about 6% and exist.
27. as each described curtain coating composition series in the paragraph 21 to 26, but wherein the 3rd curtain coating composition further comprises from by volume about 0.0% to a kind of particulate weighting agent of about 12% by volume.
28. as paragraph 27 described curtain coating composition series, wherein this trilaminar particulate weighting agent is from by volume about 0.0% to by volume about 6% and exist.
29. as each described curtain coating composition series in the paragraph 25 to 28, wherein this particulate weighting agent can be one or more weighting agents.
30. as each described curtain coating composition series in the paragraph 21 to 29, but further comprise a kind of the 4th curtain coating composition, but but but the 4th curtain coating composition comprise a kind of the 4th carrier liq and remain to be placed a kind of curtain coating fluoropolymer on this first curtain coating composition.
31. as each described curtain coating composition series in the paragraph 30, but further comprise a kind of the 5th curtain coating composition, but but but the 5th curtain coating composition comprise a kind of the 5th carrier liq and remain to be placed a kind of curtain coating fluoropolymer on the 3rd curtain coating composition.
32. as one of paragraph 30 or 31 described curtain coating composition series, wherein the 4th and the 5th carrier liq is water-based, is a kind of solvent or its mixture.
33. as each described curtain coating composition series in the paragraph 30 to 32, but wherein the 4th and the 5th curtain coating fluoropolymer is to be selected from: tetrafluoroethylene-perfluor (alkyl vinyl ether) is multipolymer or fluorizated ethylene propylene copolymer (FEP) or their mixture (PFA).
34. as each described curtain coating composition series in the paragraph 30 to 33, wherein the 4th or layer 5 further comprise from by volume about 0.0% to a kind of particulate weighting agent of about 12% by volume.
35. as paragraph 34 described curtain coating composition series, wherein this trilaminar particulate weighting agent is from by volume about 0.0% to by volume about 6% and exist.
36. as each described curtain coating composition series in the paragraph 21 to 35, wherein these multilayer film have in about 0.6 mil to the thickness between about 2 mils when removing this carrier.
37. as paragraph 36 described curtain coating composition series, wherein these multilayer film have the thickness between about 0.8 mil and about 1.5 mils.
38. as each described curtain coating composition series in the paragraph 21 to 37, wherein the dielectric breakdown strength of these multilayer film (kV) is measured as greater than 3kV by ASTM method D3755.
39. as each described curtain coating composition series in the paragraph 21 to 38, wherein the solar reflectance of these multilayer film is measured as greater than 70% by ASTM method E424.
40. as each described curtain coating composition series in the paragraph 21 to 39, wherein the steam permeating rate of these multilayer film is measured as less than about 20g/m by ASTM method F1249 2/ day.
41. as each described curtain coating composition series in the paragraph 21 to 40, wherein the light obscuration of these multilayer film is measured as greater than about 80% by ASTM method E424.
42. as each described curtain coating composition series in the paragraph 21 to 41, wherein when these multilayer film have thickness between about 0.7 mil and about 2 mils, the dielectric breakdown strength of these multilayer film (kV) is measured as greater than 3kV by ASTM method D3755, this solar reflectance is measured as greater than 70% by ASTM method E424, and this steam permeating rate is measured as less than 20g/m by ASTM method F1249 2/ day.
43. a method for preparing multilayer film may further comprise the steps: on a matrix, apply a kind of first curtain coating composition forming a first layer, but this curtain coating composition comprises a kind of first carrier liq and a kind of first curtain coating fluoropolymer; This first layer is contacted to form a second layer with a kind of second curtain coating composition, wherein but but this second curtain coating composition comprises the second curtain coating composition of a kind of second carrier liq, a kind of second curtain coating fluoropolymer and a kind of particulate filler material, but wherein this particulate filler material with from about 20% being present in this second curtain coating fluoropolymer by volume to about 45% scope by volume; And this second layer is contacted to form one the 3rd layer with a kind of the 3rd curtain coating composition, thereby make this second layer be wrapped between this first and the 3rd layer, but wherein the 3rd curtain coating composition comprise a kind of the 3rd carrier liq and a kind of the 3rd curtain coating fluoropolymer.
44. as paragraph 43 described methods, wherein this first, second and the 3rd carrier liq be water-based, be a kind of solvent or its mixture.
45. as the described method in one of paragraph 43 or 44, wherein this particulate weighting agent be with based on the cumulative volume of these multilayer film from by volume about 8% to by volume about 25% and exist.
46. as each described method in the paragraph 43 to 45, wherein this particulate weighting agent be with based on the cumulative volume of these multilayer film from by volume about 9% to by volume about 15% and exist.
47. as each described method in the paragraph 43 to 46, but wherein this first curtain coating composition further comprises from by volume about 0.0% to a kind of particulate weighting agent of about 12% by volume.
48. as paragraph 47 described methods, wherein the particulate weighting agent of this first layer is from by volume about 0.0% to by volume about 6% and exist.
49. as each described method in the paragraph 43 to 48, but wherein the 3rd curtain coating composition further comprises from by volume about 0.0% to a kind of particulate weighting agent of about 12% by volume.
50. as paragraph 49 described methods, wherein this trilaminar particulate weighting agent is from by volume about 0.0% to by volume about 6% and exist.
51. as each described method in the paragraph 47 to 50, wherein this particulate weighting agent can be one or more weighting agents.
52. as each described method in the paragraph 43 to 51, but further comprise a kind of the 4th curtain coating composition, but but but the 4th curtain coating composition comprise a kind of the 4th carrier liq and remain to be placed a kind of curtain coating fluoropolymer on this first curtain coating composition.
53. as paragraph 52 described methods, but further comprise a kind of the 5th curtain coating composition, but but but the 5th curtain coating composition comprise a kind of the 5th carrier liq and remain to be placed a kind of curtain coating fluoropolymer on the 3rd curtain coating composition.
54. as the described method in one of paragraph 52 or 53, wherein the 4th and the 5th carrier liq is water-based, is a kind of solvent or its mixture.
55. as each described method in the paragraph 52 to 54, but wherein the 4th and the 5th curtain coating fluoropolymer is to be selected from: tetrafluoroethylene-perfluor (alkyl vinyl ether) is multipolymer or fluorizated ethylene propylene copolymer (FEP) or their mixture (PFA).
56. as each described method in the paragraph 52 to 55, wherein the 4th or layer 5 further comprise from by volume about 0.0% to a kind of particulate weighting agent of about 12% by volume.
57. as paragraph 56 described methods, wherein this trilaminar particulate weighting agent is from by volume about 0.0% to by volume about 6% and exist.
58. as each described method in the paragraph 43 to 57, wherein these multilayer film have in about 0.7 mil to the thickness between about 2 mils when removing this carrier.
59. as paragraph 58 described methods, wherein these multilayer film have the thickness between about 0.8 mil and about 1.5 mils.
60. as each described method in the paragraph 43 to 59, wherein the dielectric breakdown strength of these multilayer film (kV) is measured as greater than 3kV by ASTM method D3755.
61. as each described method in the paragraph 43 to 60, wherein the solar reflectance of these multilayer film is measured as greater than 70% by ASTM method E424.
62. as each described method in the paragraph 43 to 61, wherein the steam permeating rate of these multilayer film is measured as less than about 20g/m by ASTM method F1249 2/ day.
63. as each described method in the paragraph 43 to 62, wherein the light obscuration of these multilayer film is measured as greater than about 80% by ASTM method E424.
64. as each described method in the paragraph 43 to 63, wherein when these multilayer film have thickness between about 0.8 mil and about 1.1 mils, the dielectric breakdown strength of these multilayer film (kV) is measured as greater than 3kV by ASTM method D3755, this solar reflectance is measured as greater than 70% by ASTM method E424, and this steam permeating rate is measured as less than 20g/m by ASTM method F1249 2/ day.
65. a photovoltaic device comprises a photovoltaic component and as each described any multilayer film in the paragraph 1 to 64, wherein this photovoltaic component and multilayer film are encapsulated in together.
66. as paragraph 65 described opto-electronic devices, wherein this optoelectronic component comprises a kind of photovoltaic component.
67. as paragraph 66 described photovoltaic devices, wherein these multilayer film are placed on the packaging film.
68. as paragraph 67 described photovoltaic devices, wherein this packaging film is to be selected from: ethylene vinyl acetate, ethylene methyl acrylate, thermoplastic polyurethane, polyvinyl butyral acetal, organosilicon, polyolefin polymer, polyolefin copolymer or ionomer.
Below from 1 to 68 paragraph of sequentially enumerating a plurality of still other aspect of the present invention is provided.In one embodiment, in first section (1), a kind of curtain coating composition comprises: a kind of carrier liq; A kind of matrix material of non-fibrillation; A kind of particulate filler material, wherein some particles of this particulate filler material present a single linear dimension greater than 10 μ m; And wherein this matrix material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent.
2. a curtain coating composition comprises: a kind of carrier liq; A kind of matrix material of non-fibrillation; A kind of particulate filler material, wherein some particles of this particulate filler material present a single linear dimension greater than 10 μ m; And wherein this matrix material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material less than 15 volume percent.
3. a curtain coating composition comprises: a kind of carrier liq; A kind of matrix material of non-fibrillation; A kind of particulate filler material does not wherein have particle to present a single linear dimension greater than 10 μ m in this particulate filler material; And wherein this matrix material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material less than 15 volume percent.
4. a curtain coating composition comprises: a kind of carrier liq; A kind of matrix material of non-fibrillation; A kind of particulate filler material does not wherein have particle to present a single linear dimension greater than 10 μ m in this particulate filler material; And wherein this matrix material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent.
5. a curtain coating composition comprises: a kind of carrier liq; A kind of non-fluorinated polymer substrate material of non-fibrillation; A kind of particulate filler material does not wherein have particle to present a single linear dimension greater than 10 μ m in this particulate filler material; And wherein this non-fluorinated polymer substrate material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent.
6. as each described curtain coating composition in the paragraph 1 to 5, wherein this curtain coating composition comprises a kind of a kind of the be divided into prose style free from parallelism of particle in this carrier liq of particle and this filler material of fluoropolymer.
7. as each curtain coating composition in the paragraph 1 to 6, wherein this carrier liq comprises water.
8. as each described curtain coating composition in the paragraph 1 to 7, wherein this polymkeric substance is: tetrafluoroethylene, poly(vinylidene fluoride), polychlorotrifluoroethylene, fluorinated ethylene propylene, tetrafluoroethylene/hexafluoropropylene/ethylene copolymer, chlorotrifluoroethylene/vinylidene fluoride copolymer, chlorotrifluoroethylene/R 1216, chlorotrifluoroethylene/ethylene copolymer, ethene/trifluoro-ethylene copolymer, Tefzel, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene-perfluor (alkyl vinyl ether) multipolymer or their mixture.
9. as each described curtain coating composition in the paragraph 1 to 8, wherein these filling agent particles comprise the inorganic filler particle of coating, and the inorganic filler particle of these coatings comprises an inorganic core and centers on a coat of this core.
10. as paragraph 9 described curtain coating compositions, wherein this coat is a silane coating, zirconate coating or titanate coating.
11. as each described curtain coating composition in the paragraph 1 to 10, wherein all these filling agent particles all have identical in fact granularity.
12. as each described curtain coating composition in the paragraph 1 to 11, further comprise a kind of tensio-active agent, thereby this tensio-active agent is the surface tension that is used to change this liquid makes wetting these filling agent particles of this liquid.
13. as paragraph 12 described curtain coating compositions, wherein this tensio-active agent is a kind of ionic surface active agent or a kind of nonionogenic tenside.
14. as paragraph 12 described curtain coating compositions, wherein this tensio-active agent is a kind of amphoteric or cationic tensio-active agent.
15. as each described curtain coating composition in the paragraph 1 to 14, further comprise: a kind of viscosity modifier, thereby this viscosity modifier is added into the viscosity of adjusting this curtain coating composition and postpones separating of this particulate weighting agent and said composition, so that a kind of stable, curtain coating composition uniformly is provided.
16. a film comprises: a kind of matrix material of non-fibrillation; A kind of selected particulate filler material, wherein some particles of this particulate filler material present a single linear dimension greater than 10 μ m; And wherein this matrix material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent.
17. a film comprises: a kind of matrix material of non-fibrillation; A kind of particulate filler material, wherein some particles of this particulate filler material present a single linear dimension greater than 10 μ m; And wherein this matrix material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material less than 15 volume percent.
18. a film comprises: a kind of matrix material of non-fibrillation; A kind of particulate filler material does not wherein have particle to present a single linear dimension greater than 10 μ m in this particulate filler material; And wherein this matrix material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material less than 15 volume percent.
19. a film comprises: a kind of matrix material of non-fibrillation; A kind of particulate filler material does not wherein have particle to present a single linear dimension greater than 10 μ m in this particulate filler material; And wherein this matrix material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent.
20. a film comprises: a kind of non-fluorinated polymer substrate material of non-fibrillation; A kind of particulate filler material does not wherein have particle to present a single linear dimension greater than 10 μ m in this particulate filler material; And wherein this non-fluorinated polymer substrate material and particulate filler material with for provide a kind of dried laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent.
21. as each described film in the paragraph 16 to 20, wherein this polymkeric substance is: tetrafluoroethylene, poly(vinylidene fluoride), polychlorotrifluoroethylene, fluorinated ethylene propylene, tetrafluoroethylene/hexafluoropropylene/ethylene copolymer, chlorotrifluoroethylene/vinylidene fluoride copolymer, chlorotrifluoroethylene/R 1216, chlorotrifluoroethylene/ethylene copolymer, ethene/trifluoro-ethylene copolymer, Tefzel, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene-perfluor (alkyl vinyl ether) multipolymer or their mixture.
22. as each described film in the paragraph 16 to 21, wherein these filling agent particles comprise the inorganic filler particle of coating, the inorganic filler particle of these coatings comprises an inorganic core and centers on a coat of this core.
23. as paragraph 23 described films, wherein this coat is a silane coating, zirconate coating or titanate coating.
24. as each described film in the paragraph 16 to 23, wherein each filling agent particle all is a spheric.
25. multilayer film comprise: one first fluoropolymer film; Place on this first fluoropolymer film one as paragraph 16 to 24 each described one second films; And place one the 3rd fluoropolymer film on this second film.
26. multilayer film comprise: one as each described the first film in the paragraph 16 to 24; And one as each described second film in the paragraph 16 to 24.
27., further comprise: as one or more additional layer each described film in the paragraph 16 to 23 or a kind of film as paragraph 26 described multilayer film.
28., further comprise a fluoropolymer skin as the described multilayer film in one of paragraph 26 or 27.
29. as each described multilayer film in the paragraph 26 to 28, wherein this or these fluoroplymer layer (if the words that exist) is selected from PTFE, ETFE, FEP or PFA independently of one another.
30. a photovoltaic device comprises: photovoltaic component and as paragraph 16 to 29 described any films, wherein this photovoltaic component and film are encapsulated in together.
31. a method for preparing multilayer film may further comprise the steps: a kind of curtain coating composition is coated on a kind of matrix, and this curtain coating composition comprises: a kind of carrier; A kind of matrix material of non-fibrillation; A kind of particulate filler material, wherein some particles of this particulate filler material present the single linear dimension of about 10 μ m; And wherein this matrix material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition; This laminated film is contacted with a kind of second curtain coating composition, and wherein this second curtain coating composition comprises: a kind of carrier; And a kind of matrix material, a kind of multilayer film is provided thus; And further these multilayer film are contacted with a kind of the 3rd curtain coating composition, wherein the 3rd curtain coating composition comprises: a kind of carrier; And a kind of matrix material, a kind of 3 layers multilayer film are provided thus, wherein this granular layer is between this first and the 3rd layer.
32. as paragraph 31 described methods, comprise that further one or more curtain coating compositions of a usefulness apply the step of this laminated film, this curtain coating composition comprises a kind of carrier; A kind of matrix material of non-fibrillation; A kind of particulate filler material, wherein some particles of this particulate filler material present the single linear dimension of about 10 μ m; And wherein this matrix material and particulate filler material with for provide a kind of multi-layer compound film layer effectively relative value be included in the said composition.
33., comprise further this multi-layer compound film is contacted with a kind of curtain coating composition that wherein this curtain coating composition comprises: a kind of carrier as paragraph 32 described methods; And a kind of polymer materials, provide thus to have one first outer field a kind of multilayer film.
34., comprise further this multi-layer compound film is further contacted with a kind of curtain coating composition that wherein this curtain coating composition comprises: a kind of carrier as paragraph 33 described methods; And a kind of polymer materials, provide thus to have one second outer field a kind of multilayer film, wherein these MULTILAYER COMPOSITE granular layers are between these two skins.
35., further comprise making a skin stand the step of a charged particle technology as each described method in the paragraph 31 to 34.
36. as paragraph 35 described methods, wherein this charged particle technology is corona discharge or Cement Composite Treated by Plasma.
37. as paragraph 36 described methods, wherein this corona treatment is to carry out in the presence of a kind of solvent atmosphere.
38. as paragraph 37 described methods, wherein this solvent atmosphere is a kind of ketone.
39. as paragraph 38 described photovoltaic devices, wherein these multilayer film are liners behind of this photovoltaic component.
The present invention further specifies with reference to following a plurality of limiting examples.To be clear that for those of ordinary skill in the art, and can make multiple change and not deviate from scope of the present invention these illustrated embodiments.Therefore, scope of the present invention should not be subject in this application these embodiments of explanation, and only is subjected to the restriction by the equivalent of the illustrated embodiment of the language of claim and these embodiments.Except as otherwise noted, all per-cents are by weight.
Example
The preparation of curtain coating fluoropolymer film
The general procedure of film casting
(a) use the organic or inorganic weighting agent such as a kind of white pigment (TiO 2, ZnO or other pigment described here) prepare a kind of aqueous dispersion.
(b) prepared a kind of aqueous dispersion, it comprises a kind of film-forming polymer material, and this film-forming polymer material is selected from and runs through described any in those of this specification sheets, and a kind of in particular fluoropolymer.This dispersion may contain the aqueous dispersion of describing in step (a).
(c) a carrier band dipping can be passed the dispersion of describing in the step (b) then, thereby make a coating that on this carrier band, forms this dispersion.
(d) make the carrier band of this coating pass a metering zone, to remove excessive dispersion.
(e) coated carrier after will measuring carries out drying, to remove water from this dispersion.
(f) dried coated carrier is heated to is enough to a temperature making this dispersion fixed then, wherein this carrier band is to be formed by a kind of material with low thermal mass, and this material has the yield strength that chemistry and dimensional stability and the work of adhesion between this carrier band and this dispersion are no more than this fixed fluoropolymer film under the consolidation temperature of this dispersion.
(g) can repeating step (c) to step (f) be used for curtain coating multiwalled film in case of necessity.Has a dispersion that will contain in step (a) or describe (b) in these dispersion coatings at least.
(h) can randomly this film be peeled off from this carrier (as a kind of polyimide).
(i) can be randomly, can be on one or both sides or otherwise carry out C-and handle with these multilayer film, thus make to be cohesible with this surface treatment.
Dispersion:
Have 22 volume %TiO 2The PTFE dispersion
With 3, the PTFE dispersion of 384g (Daikin, 59% solid), 1, the TiO of 772g 2Slurry (DuPont R-900TiO 2, 60% solid) and 1,400 deionized water mixed 30 minutes.The fluoroalkyl surfactants (Ciba, 60% solid) of adding 32g modification and remix are 10 minutes in this mixture.Screen cloth with one 10 microns of this solution filtrations.
Has 14.8vol%TiO 2The PTFE dispersion
With 3, the TiO of the PTFE dispersion of 000g (Daikin, 59% solid), 990g 2Slurry (DuPont R-900TiO 2, 60% solid) and 800 deionized waters mixed 30 minutes.The tensio-active agent (Ciba, 60% solid) of adding 24g modification and remix are 10 minutes in this mixture.Screen cloth with one 10 microns of this solution filtrations.
Has 12vol%TiO 2The PTFE dispersion
With 1, the TiO of the PTFE dispersion of 532g (Daikin, 59% solid), 400g 2Slurry (DuPont R-900TiO 2, 60% solid) and 550 deionized waters mixed 30 minutes.The tensio-active agent (Ciba, 60% solid) of adding 10g modification and remix are 10 minutes in this mixture.Screen cloth with one 10 microns of this solution filtrations.
Have 38 volume %TiO 2The PTFE dispersion
With 3, the PTFE dispersion of 000g (Daikin, 60% solid), 3, the TiO of 440g 2Slurry (DuPont R-900TiO 2, 60% solid) and 3, the 500g deionized water mixed 30 minutes.The fluoroalkyl surfactants (Ciba, 60% solid) of adding 50g modification and remix are 10 minutes in this mixture.Screen cloth with one 10 microns of this solution filtrations.
Have 4 volume %TiO 2The PTFE dispersion
With 7, the TiO of the PTFE dispersion of 659g (Daikin, 60% solid), 666g 2Slurry (DuPont R-900TiO 2, 60% solid) and 1, the 625g deionized water mixed 30 minutes.The fluoroalkyl surfactants (Ciba, 60% solid) of adding 50g modification and remix are 10 minutes in this mixture.Screen cloth with one 10 microns of this solution filtrations.
Have 41 volume %TiO 2The PTFE dispersion
With the PTFE dispersion (Daikin, 60% solid) of 550g, the TiO of 826g 2Slurry (DuPont R-900TiO 2, 60% solid) and the 600g deionized water mixed 30 minutes.A kind of acrylic copolymer (Rohm and Haas, 100% solid) of the fluoroalkyl surfactants (Ciba, 60% solid) of adding 10g modification and 13.2g and remix are 10 minutes in this mixture.Screen cloth with one 10 microns of this solution filtrations.
Have 28 volume %TiO 2The PTFE dispersion
With 3, the PTFE dispersion of 970g (Daikin, 60% solid), 2, the TiO of 870g 2Slurry (DuPont R-900TiO 2, 60% solid) and 3, the 110g deionized water mixed 30 minutes.The fluoroalkyl surfactants (Ciba, 60% solid) that in this mixture, adds the 50g modification.Screen cloth with one 10 microns of this solution filtrations.
Has 3% volume TiO 2The PTFE dispersion
With the PTFE dispersion (Daikin, 60% solid) of 728g, the TiO of 105g 2Slurry (DuPont R-900TiO 2, 60% solid) and the 172g deionized water mixed 30 minutes.The fluoroalkyl surfactants (Ciba, 60% solid) that in this mixture, adds the 5g modification.Screen cloth with one 10 microns of this solution filtrations.
PTFE dispersion with 2vol% carbon black
The PTFE dispersion (Daikin, 60% solid) of 816g, carbon black slurry (TOKAI Aqua black, 30% solid) and the 143g deionized water of 33g were mixed 30 minutes.In this mixture, add the fluoroalkyl surfactants (Ciba, 60% solid) of 5g modification and a kind of acrylic copolymer (Rohm and Haas, 100% solid) of 3 grams.Screen cloth with one 10 microns of this solution filtrations.
The clarifying PTFE dispersion that does not have weighting agent
PTFE dispersion (Daikin, 59% solid) and 157 deionized waters of 796g were mixed 30 minutes.Screen cloth with one 10 microns of this solution filtrations.
The clarifying PFA dispersion that does not have weighting agent
With 1, the PFA dispersion of 480g (DuPont, the solid of 58%-62%) and 2520g deionized water mixed 30 minutes.The nonionogenic tenside (DuPont, 50% solid) of adding 10g modification and remix are 10 minutes in this mixture.Screen cloth with one 10 microns of this solution filtrations.
The clarifying FEP dispersion that does not have weighting agent
With 1, the FEP dispersion of 000g (DuPont, 41% solid) and 450g deionized water mixed 30 minutes.The nonionogenic tenside (DuPont, 50% solid) of adding 2.25g modification and remix are 10 minutes in this mixture.Screen cloth with one 10 microns of this solution filtrations.
Prepared following film according to following general procedure:
Example 1
A kind of four layers film that uses general procedure described above and method to prepare to have following formation:
Has 22.0vol%TiO 2PTFE
Has 22.0vol%TiO 2PTFE
Has 22.0vol%TiO 2PTFE
FEP (filler-free)
Total film thickness: 1.1 mils
Example 2
A kind of five layers film that uses general procedure described above and method to prepare to have following formation:
PTFE (filler-free)
Has 14.8vol%TiO 2PTFE
Has 14.8vol%TiO 2PTFE
Has 14.8vol%TiO 2PTFE
FEP (filler-free)
Total film thickness: 1.1 mils
Example 3
Has 12vol%TiO 2PTFE
Has 12vol%TiO 2PTFE
Has 12vol%TiO 2PTFE
FEP (filler-free)
Total film thickness: 1.1 mils
Measured following characteristic:
Figure BDA0000063309770000401
Tedlar PV2111 be a kind of commercial film of selling by DuPont and be used for PV after the liner rhythmo structure.Film thickness is 1.0 mils.
For liner film behind the PV of one 1 mil, the value＞=3.00kV of dielectric breakdown strength generally is considered as acceptable.
Testing method:
The dielectric breakdown strength observed value uses Beckman dielectrometer QC101A to measure according to ASTM D149 generally.Film is placed between the circular electrode with 0.25 inch diameter.Apply the dc voltage of inclination then with constant inclination speed (typically 500V/s) from zero volt beginning.Voltage when observing film thickness and burnt is reported as dielectric breakdown voltage.
Optical transmittance is to use a Gretag Macbeth according to ASTM E424
Figure BDA0000063309770000411
7000A is Spectrophotometric.Wavelength scanning range is 400nm-750nm.To make beam orifice be empty and make the reflectivity standards thing carry out background correction scanning in reflection hole.Then film is loaded in the beam orifice of annex and has measured % total transmittance (diffusion+regular transmission).Opaqueness %=100%-transmissivity %.
Example 4
A kind of five layers film that uses general procedure described above and method to prepare to have following formation:
Form Thickness (mil)
The PFA-filler-free 0.10
The PTFE-filler-free 0.35
Has 38Vol%TiO 2PTFE 0.35
Has 4Vol%TiO 2PTFE 0.20
The FEP-filler-free 0.10
Amount to (9.6Vol%TiO 2) 1.10
Example 5
A kind of five layers film that uses general procedure described above and method to prepare to have following formation:
Form Thickness (mil)
The PFA-filler-free 0.03
The PTFE-filler-free 0.35
Has 41Vol%TiO 2PTFE 0.35
The PTFE filler-free 0.25
The FEP-filler-free 0.03
Amount to (11.6 Vol%TiO 2) 1.01
Example 6
A kind of trilaminar film that uses general procedure described above and method to prepare to have following formation:
Form Thickness (mil)
Has 22Vol%TiO 2PTFE 0.35
Has 22Vol%TiO 2PTFE 0.35
The FEP-filler-free 0.20
Amount to (16.4 Vol%TiO 2) 0.90
The characteristic that records
Example 7
A kind of five layers film that uses general procedure described above and method to prepare to have following formation:
Form Thickness (mil)
The PFA-filler-free 0.05
The PTFE-filler-free 0.25
Has 28Vol%TiO 2PTFE 0.40
Has 3Vol%TiO 2PTFE 0.25
The FEP-filler-free 0.05
Amount to (10.5Vol%TiO 2) 1.0
Figure BDA0000063309770000431
Example 8
A kind of five layers film that uses general procedure described above and method to prepare to have following formation:
Form Thickness (mil)
The PFA-filler-free 0.05
The PTFE-filler-free 0.25
Has 28Vol%TiO 2PTFE 0.40
PTFE with 2vol% carbon black 0.15
The FEP-filler-free 0.05
Amount to (10.9Vol%TiO 2) 0.90
Figure BDA0000063309770000432
Example 4 to 8 is performed as follows test: dielectric breakdown strength is to measure according to ASTM D3755 (being used for the dielectric breakdown voltage of solid electrically insulating material and the standard method of test of dielectric strength under DC voltage stress); Solar reflectance is to measure according to ASTM E424 (being used for the solar energy transmission of sheeting and the standard method of test of reflectivity (land)); Steam permeating rate is to measure according to ASTM F1249 (using a kind of synthetic infrared sensor to pass the steam permeating rate of plastics film and sheet material); And opaqueness is measured according to ASTM method E424.
Although describe the present invention with reference to embodiment preferred, those of ordinary skill in the art will recognize, can make multiple change in form and details and not deviate from the spirit and scope of the present invention.Run through all reference that this specification sheets is quoted, comprise in the background those, all be combined in this in full with it.Those of ordinary skill in the art will recognize or only use not transnormal experiment just can determine a plurality of equivalents in this specific embodiments of the present invention that definitely illustrates.These equivalents are intended to be included among the scope of following these claims.

Claims (37)

1. film comprises:
A kind of fluoropolymer substrate material of non-fibrillation;
A kind of particulate filler material does not wherein have particle to present a single linear dimension greater than 10 μ m in this particulate filler material; And wherein
This fluoropolymer substrate material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material less than 15 volume percent.
2. film as claimed in claim 1, wherein this fluoropolymer is to be selected from: tetrafluoroethylene, poly(vinylidene fluoride), polychlorotrifluoroethylene, fluorinated ethylene propylene, tetrafluoroethylene/hexafluoropropylene/ethylene copolymer, chlorotrifluoroethylene/vinylidene fluoride copolymer, chlorotrifluoroethylene/R 1216, chlorotrifluoroethylene/ethylene copolymer, ethene/trifluoro-ethylene copolymer, Tefzel, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene-perfluor (alkyl vinyl ether) multipolymer or their mixture.
3. opto-electronic device comprises:
Optoelectronic component and the described film of claim 2, wherein this optoelectronic component and this film are encapsulated in together.
4. opto-electronic device as claimed in claim 3, wherein this film is a liner behind of this optoelectronic component.
5. film comprises:
A kind of fluoropolymer substrate material of non-fibrillation;
A kind of particulate filler material does not wherein have particle to present a single linear dimension greater than 10 μ m in this particulate filler material; And wherein
This fluoropolymer substrate material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent.
6. film as claimed in claim 5, wherein this fluoropolymer is to be selected from: tetrafluoroethylene, poly(vinylidene fluoride), polychlorotrifluoroethylene, fluorinated ethylene propylene, tetrafluoroethylene/hexafluoropropylene/ethylene copolymer, chlorotrifluoroethylene/vinylidene fluoride copolymer, chlorotrifluoroethylene/R 1216, chlorotrifluoroethylene/ethylene copolymer, ethene/trifluoro-ethylene copolymer, Tefzel, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene-perfluor (alkyl vinyl ether) multipolymer or their mixture.
7. opto-electronic device comprises:
Optoelectronic component and the described film of claim 6, wherein this optoelectronic component and this film are encapsulated in together.
8. opto-electronic device as claimed in claim 7, wherein this layer film is a liner behind of this optoelectronic component.
9. multilayer film comprise:
One first fluoropolymer film;
One second film, this second film comprises a kind of fluoropolymer substrate material of non-fibrillation;
A kind of particulate filler material does not wherein have particle to present a single linear dimension greater than 10 μ m in this particulate filler material; And wherein
This fluoropolymer substrate material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material less than 15 volume percent; And
Place one the 3rd fluoropolymer film on this second film.
10. multilayer film as claimed in claim 9, wherein this fluoropolymer substrate material is to be selected from: tetrafluoroethylene, poly(vinylidene fluoride), polychlorotrifluoroethylene, fluorinated ethylene propylene, tetrafluoroethylene/hexafluoropropylene/ethylene copolymer, chlorotrifluoroethylene/vinylidene fluoride copolymer, chlorotrifluoroethylene/R 1216, chlorotrifluoroethylene/ethylene copolymer, ethene/trifluoro-ethylene copolymer, Tefzel, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene-perfluor (alkyl vinyl ether) multipolymer or their mixture.
11. multilayer film as claimed in claim 10, wherein these fluoroplymer layers are selected from independently of one another: polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluor (alkyl vinyl ether) multipolymer (PFA), Tefzel (ETFE), fluorizated ethylene propylene copolymer (FEP), poly(vinylidene fluoride) (PVDF), polychlorotrifluoroethylene (PCTFE) or their mixture.
12. an opto-electronic device comprises:
Optoelectronic component and the described multilayer film of claim 11, wherein this optoelectronic component and this film are encapsulated in together.
13. opto-electronic device as claimed in claim 12, wherein these multilayer film are liners behind of this optoelectronic component.
14. multilayer film comprise:
One first fluoropolymer film;
One second film, this second film comprises: a kind of fluoropolymer substrate material of non-fibrillation;
A kind of particulate filler material does not wherein have particle to present a single linear dimension greater than 10 μ m in this particulate filler material; And wherein
This fluoropolymer substrate material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition, this laminated film comprises the filler material greater than 15 volume percent; And
Place one the 3rd fluoropolymer film on this second film.
15. multilayer film as claimed in claim 14, wherein this fluoropolymer substrate material is to be selected from: tetrafluoroethylene, poly(vinylidene fluoride), polychlorotrifluoroethylene, fluorinated ethylene propylene, tetrafluoroethylene/hexafluoropropylene/ethylene copolymer, chlorotrifluoroethylene/vinylidene fluoride copolymer, chlorotrifluoroethylene/R 1216, chlorotrifluoroethylene/ethylene copolymer, ethene/trifluoro-ethylene copolymer, Tefzel, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene-perfluor (alkyl vinyl ether) multipolymer or their mixture.
16. multilayer film as claimed in claim 15, wherein these fluoroplymer layers are selected from independently of one another: polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluor (alkyl vinyl ether) multipolymer (PFA), Tefzel (ETFE), fluorizated ethylene propylene copolymer (FEP), poly(vinylidene fluoride) (PVDF), polychlorotrifluoroethylene (PCTFE) or their mixture.
17. an opto-electronic device comprises:
Optoelectronic component and the described multilayer film of claim 16, wherein this optoelectronic component and these multilayer film are encapsulated in together.
18. a method for preparing multilayer film may further comprise the steps:
A kind of curtain coating composition is coated on a kind of matrix, and this curtain coating composition comprises:
A kind of carrier;
A kind of fluoropolymer substrate material of non-fibrillation;
A kind of particulate filler material; And
Wherein this fluoropolymer substrate material and particulate filler material with for provide a kind of laminated film effectively relative value be included in the said composition;
This laminated film is contacted with a kind of second curtain coating composition, and wherein this second curtain coating composition comprises:
A kind of carrier; And
Matrix material provides a kind of multilayer film thus; And
Further this laminated film is contacted with a kind of the 3rd curtain coating composition, wherein the 3rd curtain coating composition comprises:
A kind of carrier; And
A kind of matrix material provides a kind of 3 layers multilayer film thus, and wherein this composite bed is between this first and the 3rd layer.
19. method as claimed in claim 18 further comprises a step that applies this laminated film with one or more curtain coating compositions, this curtain coating composition comprises:
A kind of carrier;
A kind of fluoropolymer substrate material of non-fibrillation;
A kind of particulate filler material; And
Wherein this matrix material and particulate filler material with for provide a kind of THIN COMPOSITE rete effectively relative value be included in the said composition.
20. method as claimed in claim 19 comprises further this multi-layer compound film is contacted with a kind of curtain coating composition that wherein this curtain coating composition comprises:
A kind of carrier; And
Fluoropolymer material provides to have one first outer field a kind of multilayer film thus.
21. method as claimed in claim 20 comprises further this multi-layer compound film is further contacted with a kind of curtain coating composition that wherein this curtain coating composition comprises:
A kind of carrier; And
A kind of fluoropolymer material provides to have one second outer field a kind of multilayer film thus, and wherein these multiwalled composite particles layers are between these two skins.
22. method as claimed in claim 21 further may further comprise the steps:
Make a skin stand a charged particle technology.
23. method as claimed in claim 22, wherein this charged particle technology is corona discharge or Cement Composite Treated by Plasma.
24. multilayer film comprise:
A first layer, this first layer comprise a kind of water-based or the castable fluoropolymer of solvent or its mixture;
Place a second layer on this first layer, this second layer comprises a kind of water-based or the castable fluoropolymer of solvent or its mixture and a kind of particulate filler material or its mixture, wherein
This particulate filler material is with from about 10% being present in this castable fluoropolymer to about 45% scope by volume by volume; And
Place the 3rd layer on this second layer, the 3rd layer comprises a kind of water-based or the castable fluoropolymer of solvent or its mixture.
25. multilayer film as claimed in claim 24 further comprise one the 4th layer that is placed on this first layer, the 4th layer comprises a kind of water-based or the castable fluoropolymer of solvent or its mixture.
26. multilayer film as claimed in claim 25 further comprise a layer 5 that places on the 3rd layer, this layer 5 comprises a kind of water-based or the castable fluoropolymer of solvent or its mixture.
27. multilayer film as claimed in claim 26, wherein the 4th and layer 5 be to be selected from: polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluor (alkyl vinyl ether) multipolymer (PFA), Tefzel (ETFE), fluorizated ethylene propylene copolymer (FEP), poly(vinylidene fluoride) (PVDF), polychlorotrifluoroethylene (PCTFE) or their mixture.
28. multilayer film as claimed in claim 24, wherein this dielectric breakdown strength (kV) is measured as greater than 3kV by ASTM method D3755.
29. multilayer film as claimed in claim 24, wherein this solar reflectance is measured as greater than 70% by ASTM method E424.
30. multilayer film as claimed in claim 24, wherein this steam permeating rate is measured as less than about 20g/m by ASTM method F1249 2/ day.
31. multilayer film as claimed in claim 24, wherein this light obscuration is measured as greater than about 80% by ASTM method E424.
32. multilayer film as claimed in claim 24, wherein this solar reflectance is greater than 30% in infra-red range.
33. multilayer film as claimed in claim 24, wherein this solar reflectance is greater than 50% in infra-red range.
34. multilayer film as claimed in claim 24, wherein this solar reflectance is greater than 70% in infra-red range.
35. it is greater than 90% that multilayer film as claimed in claim 25, one of them mask have greater than 65% high-reflectivity and total opaqueness of this film.
36. it is greater than 95% that multilayer film as claimed in claim 25, one of them mask have greater than 70% high-reflectivity and total opaqueness of this film.
37. it is greater than 99% that multilayer film as claimed in claim 25, one of them mask have greater than 75% high-reflectivity and total opaqueness of this film.
CN2009801468618A 2008-10-13 2009-10-12 Fluoropolymer/particulate filled protective sheet Pending CN102224189A (en)

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CN103897392A (en) * 2012-12-31 2014-07-02 中原工学院 Fluoridated polyimide film for thin-film solar cells and preparation method thereof
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